CN108751179B - Preparation method of transparent graphene conductive film - Google Patents
Preparation method of transparent graphene conductive film Download PDFInfo
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- C01B32/00—Carbon; Compounds thereof
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Abstract
The invention discloses a preparation method of a transparent graphene conductive film, and belongs to the technical field of conductive materials. Introducing carbon dioxide into the polyallylamine mixture at a speed of 20-30 mL/min, and stirring and mixing for 20-30 min at a temperature of 40-45 ℃ and a rotating speed of 250-300 r/min to obtain a mixture; mixing the mixture with hydrazine hydrate according to a mass ratio of 8: 1-10: 1, mixing, performing ultrasonic dispersion for 15-20 min under the condition of the frequency of 55-65 kHz, and stirring and reacting for 2-4 h under the conditions of the temperature of 45-55 ℃ and the rotating speed of 380-450 r/min to obtain blank liquid; and carrying out vacuum filtration on the blank liquid to obtain a transparent graphene conductive film blank, and drying the transparent graphene conductive film blank at the temperature of 65-75 ℃ for 2-3 h to obtain the transparent graphene conductive film. The transparent graphene conductive film obtained by the invention has excellent conductivity.
Description
Technical Field
The invention discloses a preparation method of a transparent graphene conductive film, and belongs to the technical field of conductive materials.
Background
The conductive polymer can be classified into a structural type (intrinsic type) and a composite type (doped type) according to the composition and the conductive mechanism. The composite conductive polymer gradually becomes a conductive material with active research, rapid development and wide application by virtue of obvious advantages in the aspects of conductivity, stability, processability and the like. The conductive filler is added into a non-conductive polymer matrix to realize conductivity, the conductive mechanism of the conductive filler is that the conductive fillers in the matrix are generally considered to be in mutual contact to form a continuous conductive network, and current carriers can move in the network, so that the graphene oxide composite conductive film is conductive. The conductive fillers generally used include carbon fillers, metal oxide fillers and composite fillers. The carbon filler has the advantages of low cost, easily obtained raw materials, small density, stable property, environmental friendliness and the like, and the proportion of the carbon filler is increased day by day in the selection and use of the conductive filler.
Transparent Conductive Films (TCFs) are important components of optoelectronic devices such as touch screens, displays, solar cells, and the like. Indium Tin Oxide (ITO) is widely used in these optoelectronic devices, but it lacks flexibility, is difficult to deposit on flexible substrates, and is difficult to meet the requirements of the times. In this regard, many other materials have been tried to replace ITO, such as: carbon nanotubes, conductive polymers, silver (or copper) nanowires, etc., but each has advantages and disadvantages. For noble metal nanowires, the purity of the nanowires, as well as the radius size and aspect ratio, largely influence the performance of the nanowire-based transparent conductive layer. In addition, the application of the transparent conductive film is limited because the photoelectric substrate is brittle and not easy to deform. Compared with a transparent conductive film with a hard substrate, the transparent conductive film prepared on the organic flexible substrate not only has the same photoelectric characteristics, but also has a plurality of unique advantages, such as: the flexible, light in weight, difficult broken, can adopt roll-to-roll industrialization continuous production mode to be favorable to raising the efficiency, be convenient for transportation etc.. The conventional conductive film still has a problem that the conductivity cannot be further improved, and therefore research on the conductive film is needed.
Disclosure of Invention
The invention mainly solves the technical problems that: aiming at the problems that the traditional graphene conductive film is poor in transparency and the conductivity cannot be further improved, the preparation method of the transparent graphene conductive film is provided.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
(1) mixing graphene oxide and water according to a mass ratio of 1: 200-1: 300, mixing, performing ultrasonic dispersion, adding an amination agent with the mass of 0.3-0.5 of graphene oxide, and stirring for reaction to obtain an aminated graphene oxide mixture;
(2) mixing polyallylamine hydrochloride and water according to a mass ratio of 1: 100-1: 150, adjusting the pH value to 9.8-10.0 to obtain a polyallylamine hydrochloride solution, introducing nitrogen into the polyallylamine hydrochloride solution, dripping a modified glucose mixture with the mass 1.0-1.5 times that of the polyallylamine hydrochloride solution into the polyallylamine hydrochloride solution under the condition of violent stirring to obtain a pretreatment additive blank after stirring reaction, and mixing the pretreatment additive blank with sodium borohydride according to the mass ratio of 20: 1-30: 1, mixing, stirring and mixing under the nitrogen atmosphere to obtain an additive blank, and dialyzing the additive blank to obtain an additive;
(3) mixing an aminated graphene oxide mixture and a silver ammonia solution according to a mass ratio of 5: 1-10: 1, adding an additive with the mass of 0.1-0.2 times of that of the aminated graphene oxide mixture and polyallylamine with the mass of 0.2-0.3 times of that of the aminated graphene oxide mixture, and stirring and mixing to obtain a polyallylamine mixture;
(4) introducing carbon dioxide into the polyallylamine mixture, and stirring and mixing to obtain a mixture; mixing the mixture with hydrazine hydrate according to a mass ratio of 8: 1-10: 1, mixing, ultrasonically dispersing, and stirring for reaction to obtain a blank liquid;
(5) and carrying out vacuum filtration on the blank liquid to obtain a transparent graphene conductive film blank, and drying the transparent graphene conductive film blank to obtain the transparent graphene conductive film.
The amination agent in the step (1) is any one of ethylenediamine, triethylene tetramine or diethylenetriamine.
The modified glucose mixture in the step (2) is prepared by mixing glucose and water according to the mass ratio of 1: 20-1: 25, adding potassium iodate with the mass being 0.1-0.2 times that of glucose, stirring and mixing to obtain a glucose mixed solution, mixing the glucose mixed solution with a barium chloride solution according to the mass ratio of 1: 3-1: 5, mixing and filtering to obtain a filtrate, and mixing the filtrate with a sodium sulfate solution according to a mass ratio of 1: 3-1: 4, mixing, filtering and removing filter cakes to obtain the modified glucose mixture.
And (3) preparing the silver ammonia solution by mixing silver nitrate and water according to the mass ratio of 1: 10-1: 30, and dropwise adding ammonia water until all precipitates disappear to obtain a silver-ammonia solution.
The invention has the beneficial effects that:
(1) firstly, the additive contains effective components of a microgel structure, and after the additive is added into a product, amino graphene oxide can enter an interlayer structure of aminated graphene in the process of self-polymerization of formed aminated graphene due to pi-pi bonds after being reduced, so that the self-polymerization phenomenon of the aminated graphene is reduced, the number of layers of the aminated graphene in the preparation process of the product is reduced, and the transparency of the product is improved due to the transparent effective components; secondly, because the active ingredients of the microgel structure are sensitive to pH, in the preparation process of the product, along with reduction of a silver-ammonia solution, the generated ammonia is partially dissolved in water, so that the pH of the system is increased, the active ingredients are expanded, the generated nano silver particles are adsorbed, and the nano silver particles are brought into an interlayer structure of aminated graphene, so that the conductivity of the product is improved;
(2) the silver ammonia solution and the polyallylamine are added when the transparent graphene conductive film is prepared, on one hand, the added polyallylamine can be crosslinked with the polyallylamine hydrochloride in the additive under the action of carbon dioxide, so that a crosslinked network is formed in a system, the aminated graphene oxide is fixed in a network structure, the rapid agglomeration of the aminated graphene oxide in the reduction process is avoided, and the transparency of the product is improved, on the other hand, the added silver ammonia solution can be reduced by hydrazine hydrate in the preparation process of the product to form nano silver particles, ammonia gas and nitrogen gas are partially dissolved in water, the pH value of the system is improved, the effective components in the additive are expanded, the formed nitrogen gas can enable the polyallylamine and the polyallylamine hydrochloride which form the crosslinked network under the carbon dioxide to be subjected to decrosslinking, so that the carbon dioxide is generated, and the decrosslinking is carried out, the aminated graphene oxide is gradually reduced into aminated graphene and generates self-polymerization, and the generated nano silver can be fixed in an aminated graphene interlayer structure while self-polymerization is performed, so that the agglomeration of nano silver particles is reduced, the dispersibility of the nano silver is improved, the agglomeration of the aminated graphene is reduced to a certain extent, and the conductivity of the product is improved.
Detailed Description
Mixing glucose and water according to a mass ratio of 1: 20-1: 25, adding potassium iodate with the mass being 0.1-0.2 time that of glucose into a beaker, stirring and mixing for 40-60 min at the temperature of 30-45 ℃ and the rotating speed of 300-400 r/min to obtain a glucose mixed solution, mixing the glucose mixed solution with a barium chloride solution with the mass fraction of 12-18% according to the mass ratio of 1: 3-1: 5, mixing, stirring and mixing for 30-50 min at the temperature of 30-45 ℃ and the rotating speed of 250-400 r/min, filtering to obtain a filtrate, mixing the filtrate with a sodium sulfate solution with the mass fraction of 15-20% according to the mass ratio of 1: 3-1: 4, mixing, stirring and mixing for 35-45 min at the temperature of 30-45 ℃ and the rotating speed of 250-400 r/min, filtering, and removing a filter cake to obtain a modified glucose mixture; mixing graphene oxide and water according to a mass ratio of 1: 200-1: 300, performing ultrasonic dispersion for 20-30 min under the condition that the frequency is 45-65 kHz, adding an amination agent with the mass of 0.3-0.5 of graphene oxide into the mixture of the graphene oxide and water, and stirring and reacting for 8-10 h under the conditions that the temperature is 45-60 ℃ and the rotating speed is 300-350 r/min to obtain an aminated graphene oxide mixture; mixing polyallylamine hydrochloride and water according to a mass ratio of 1: 100-1: 150, stirring and mixing for 30-40 min under the conditions that the temperature is 45-55 ℃ and the rotating speed is 300-400 r/min, adjusting the pH value of a mixture of polyallylamine hydrochloride and water to 9.8-10.0 by using a sodium hydroxide solution with the mass fraction of 10-15% to obtain a polyallylamine hydrochloride solution, introducing nitrogen into the polyallylamine hydrochloride solution at the speed of 20-30 mL/min, dripping a modified glucose mixture with the mass of 1.0-1.5 times that of the polyallylamine hydrochloride solution into the polyallylamine hydrochloride solution at the speed of 5-10 mL/min under the condition that the rotating speed is 800-1200 r/min, stirring and reacting for 2-4 h under the conditions that the temperature is 30-40 ℃ and the rotating speed is 300-400 r/min to obtain a pretreatment additive blank, and mixing the pretreatment additive blank with sodium borohydride according to the mass ratio of 20: 1-30: 1, mixing the mixture in a three-neck flask, introducing nitrogen into the three-neck flask at the speed of 10-30 mL/min, stirring and reacting for 10-12 h under the conditions that the temperature is 45-65 ℃ and the rotating speed is 300-380 r/min to obtain an additive blank, and dialyzing the additive blank for 10-20 h by using a dialysis bag with the cut-off molecular weight of 10000 to obtain an additive; mixing an aminated graphene oxide mixture and a silver ammonia solution according to a mass ratio of 5: 1-10: 1, mixing the mixture in a four-neck flask, adding an additive with the mass of 0.1-0.2 time of that of an aminated graphene oxide mixture and polyallylamine with the mass of 0.2-0.3 time of that of the aminated graphene oxide mixture into the four-neck flask, and stirring and mixing the mixture for 30-50 min under the conditions that the temperature is 45-55 ℃ and the rotating speed is 300-500 r/min to obtain a polyallylamine mixture; introducing carbon dioxide into the polyallylamine mixture at a speed of 20-30 mL/min, and stirring and mixing for 20-30 min at a temperature of 40-45 ℃ and a rotating speed of 250-300 r/min to obtain a mixture; mixing the mixture with hydrazine hydrate according to a mass ratio of 8: 1-10: 1, mixing, performing ultrasonic dispersion for 15-20 min under the condition of the frequency of 55-65 kHz, and stirring and reacting for 2-4 h under the conditions of the temperature of 45-55 ℃ and the rotating speed of 380-450 r/min to obtain blank liquid; and carrying out vacuum filtration on the blank liquid to obtain a transparent graphene conductive film blank, and drying the transparent graphene conductive film blank at the temperature of 65-75 ℃ for 2-3 h to obtain the transparent graphene conductive film. The amination agent is any one of ethylenediamine, triethylene tetramine or diethylenetriamine. The silver ammonia solution is prepared by mixing silver nitrate and water according to a mass ratio of 1: 10-1: 30, and dropwise adding ammonia water with the mass fraction of 15-20% until all precipitates disappear to obtain a silver-ammonia solution.
Example 1
Mixing glucose and water according to a mass ratio of 1: 25, mixing the mixture in a beaker, adding potassium iodate with the mass 0.2 time that of glucose into the beaker, stirring and mixing the mixture for 60min at the temperature of 45 ℃ and the rotating speed of 400r/min to obtain a glucose mixed solution, mixing the glucose mixed solution with a barium chloride solution with the mass fraction of 18% according to the mass ratio of 1: 5, mixing, stirring and mixing for 50min at the temperature of 45 ℃ and the rotating speed of 400r/min, filtering to obtain a filtrate, and mixing the filtrate with a sodium sulfate solution with the mass fraction of 20% according to the mass ratio of 1: 4, mixing, stirring and mixing for 45min at the temperature of 45 ℃ and the rotating speed of 400r/min, filtering, and removing a filter cake to obtain a modified glucose mixture; mixing graphene oxide and water according to a mass ratio of 1: 300, performing ultrasonic dispersion for 30min under the condition that the frequency is 65kHz, adding an amination agent with the mass of 0.5 of graphene oxide into the mixture of the graphene oxide and water, and stirring and reacting for 10h under the conditions that the temperature is 60 ℃ and the rotating speed is 350r/min to obtain an aminated graphene oxide mixture; mixing polyallylamine hydrochloride and water according to a mass ratio of 1: 150, stirring and mixing for 40min at the temperature of 55 ℃ and the rotating speed of 400r/min, adjusting the pH value of a mixture of polyallylamine hydrochloride and water to 10.0 by using a sodium hydroxide solution with the mass fraction of 15% to obtain a polyallylamine hydrochloride solution, introducing nitrogen into the polyallylamine hydrochloride solution at the speed of 30mL/min, dripping a modified glucose mixture with the mass of 1.5 times that of the polyallylamine hydrochloride solution into the polyallylamine hydrochloride solution at the speed of 10mL/min under the rotating speed of 1200r/min, stirring and reacting for 4h at the temperature of 40 ℃ and the rotating speed of 400r/min to obtain a pretreatment additive blank, and mixing the pretreatment additive blank with sodium borohydride according to the mass ratio of 30: 1, mixing the mixture in a three-neck flask, introducing nitrogen into the three-neck flask at the rate of 30mL/min, stirring and reacting for 12 hours at the temperature of 65 ℃ and the rotating speed of 380r/min to obtain an additive blank, and dialyzing the additive blank for 20 hours by using a dialysis bag with the cut-off molecular weight of 10000 to obtain an additive; mixing an aminated graphene oxide mixture and a silver ammonia solution according to a mass ratio of 10: 1, mixing the mixture in a four-neck flask, adding an additive which is 0.2 times of the mass of the aminated graphene oxide mixture and polyallylamine which is 0.3 times of the mass of the aminated graphene oxide mixture into the four-neck flask, and stirring and mixing for 50min under the conditions that the temperature is 55 ℃ and the rotating speed is 500r/min to obtain a polyallylamine mixture; introducing carbon dioxide into the polyallylamine mixture at the speed of 30mL/min, and stirring and mixing for 30min under the conditions that the temperature is 45 ℃ and the rotating speed is 300r/min to obtain a mixture; mixing the mixture with hydrazine hydrate according to the mass ratio of 10: 1, mixing, performing ultrasonic dispersion for 20min under the condition of 65kHz frequency, and stirring and reacting for 4h under the conditions of 55 ℃ and 450r/min of rotation speed to obtain blank liquid; and carrying out vacuum filtration on the blank liquid to obtain a transparent graphene conductive film blank, and drying the transparent graphene conductive film blank at the temperature of 75 ℃ for 3h to obtain the transparent graphene conductive film. The aminating agent is ethylenediamine. The silver ammonia solution is prepared by mixing silver nitrate and water according to a mass ratio of 1: 30, and dropwise adding ammonia water with the mass fraction of 20% until all precipitates disappear to obtain a silver-ammonia solution.
Example 2
Mixing glucose and water according to a mass ratio of 1: 25, mixing the mixture in a beaker, adding potassium iodate with the mass 0.2 time that of glucose into the beaker, stirring and mixing the mixture for 60min at the temperature of 45 ℃ and the rotating speed of 400r/min to obtain a glucose mixed solution, mixing the glucose mixed solution with a barium chloride solution with the mass fraction of 18% according to the mass ratio of 1: 5, mixing, stirring and mixing for 50min at the temperature of 45 ℃ and the rotating speed of 400r/min, filtering to obtain a filtrate, and mixing the filtrate with a sodium sulfate solution with the mass fraction of 20% according to the mass ratio of 1: 4, mixing, stirring and mixing for 45min at the temperature of 45 ℃ and the rotating speed of 400r/min, filtering, and removing a filter cake to obtain a modified glucose mixture; mixing graphene oxide and water according to a mass ratio of 1: 300, performing ultrasonic dispersion for 30min under the condition that the frequency is 65kHz, adding an amination agent with the mass of 0.5 of graphene oxide into the mixture of the graphene oxide and water, and stirring and reacting for 10h under the conditions that the temperature is 60 ℃ and the rotating speed is 350r/min to obtain an aminated graphene oxide mixture; mixing an aminated graphene oxide mixture and a silver ammonia solution according to a mass ratio of 10: 1, mixing the mixture in a four-neck flask, adding polyallylamine with the mass being 0.3 time that of the aminated graphene oxide mixture into the four-neck flask, and stirring and mixing for 50min under the conditions that the temperature is 55 ℃ and the rotating speed is 500r/min to obtain a polyallylamine mixture; introducing carbon dioxide into the polyallylamine mixture at the speed of 30mL/min, and stirring and mixing for 30min under the conditions that the temperature is 45 ℃ and the rotating speed is 300r/min to obtain a mixture; mixing the mixture with hydrazine hydrate according to the mass ratio of 10: 1, mixing, performing ultrasonic dispersion for 20min under the condition of 65kHz frequency, and stirring and reacting for 4h under the conditions of 55 ℃ and 450r/min of rotation speed to obtain blank liquid; and carrying out vacuum filtration on the blank liquid to obtain a transparent graphene conductive film blank, and drying the transparent graphene conductive film blank at the temperature of 75 ℃ for 3h to obtain the transparent graphene conductive film. The aminating agent is ethylenediamine. The silver ammonia solution is prepared by mixing silver nitrate and water according to a mass ratio of 1: 30, and dropwise adding ammonia water with the mass fraction of 20% until all precipitates disappear to obtain a silver-ammonia solution.
Example 3
Mixing glucose and water according to a mass ratio of 1: 25, mixing the mixture in a beaker, adding potassium iodate with the mass 0.2 time that of glucose into the beaker, stirring and mixing the mixture for 60min at the temperature of 45 ℃ and the rotating speed of 400r/min to obtain a glucose mixed solution, mixing the glucose mixed solution with a barium chloride solution with the mass fraction of 18% according to the mass ratio of 1: 5, mixing, stirring and mixing for 50min at the temperature of 45 ℃ and the rotating speed of 400r/min, filtering to obtain a filtrate, and mixing the filtrate with a sodium sulfate solution with the mass fraction of 20% according to the mass ratio of 1: 4, mixing, stirring and mixing for 45min at the temperature of 45 ℃ and the rotating speed of 400r/min, filtering, and removing a filter cake to obtain a modified glucose mixture; mixing graphene oxide and water according to a mass ratio of 1: 300, performing ultrasonic dispersion for 30min under the condition that the frequency is 65kHz, adding an amination agent with the mass of 0.5 of graphene oxide into the mixture of the graphene oxide and water, and stirring and reacting for 10h under the conditions that the temperature is 60 ℃ and the rotating speed is 350r/min to obtain an aminated graphene oxide mixture; mixing polyallylamine hydrochloride and water according to a mass ratio of 1: 150, stirring and mixing for 40min at the temperature of 55 ℃ and the rotating speed of 400r/min, adjusting the pH value of a mixture of polyallylamine hydrochloride and water to 10.0 by using a sodium hydroxide solution with the mass fraction of 15% to obtain a polyallylamine hydrochloride solution, introducing nitrogen into the polyallylamine hydrochloride solution at the speed of 30mL/min, dripping a modified glucose mixture with the mass of 1.5 times that of the polyallylamine hydrochloride solution into the polyallylamine hydrochloride solution at the speed of 10mL/min under the rotating speed of 1200r/min, stirring and reacting for 4h at the temperature of 40 ℃ and the rotating speed of 400r/min to obtain a pretreatment additive blank, and mixing the pretreatment additive blank with sodium borohydride according to the mass ratio of 30: 1, mixing the mixture in a three-neck flask, introducing nitrogen into the three-neck flask at the rate of 30mL/min, stirring and reacting for 12 hours at the temperature of 65 ℃ and the rotating speed of 380r/min to obtain an additive blank, and dialyzing the additive blank for 20 hours by using a dialysis bag with the cut-off molecular weight of 10000 to obtain an additive; adding the aminated graphene oxide mixture into a four-neck flask, adding an additive which is 0.2 times of the mass of the aminated graphene oxide mixture and polyallylamine which is 0.3 times of the mass of the aminated graphene oxide mixture into the four-neck flask, and stirring and mixing for 50min under the conditions that the temperature is 55 ℃ and the rotating speed is 500r/min to obtain a polyallylamine mixture; introducing carbon dioxide into the polyallylamine mixture at the speed of 30mL/min, and stirring and mixing for 30min under the conditions that the temperature is 45 ℃ and the rotating speed is 300r/min to obtain a mixture; mixing the mixture with hydrazine hydrate according to the mass ratio of 10: 1, mixing, performing ultrasonic dispersion for 20min under the condition of 65kHz frequency, and stirring and reacting for 4h under the conditions of 55 ℃ and 450r/min of rotation speed to obtain blank liquid; and carrying out vacuum filtration on the blank liquid to obtain a transparent graphene conductive film blank, and drying the transparent graphene conductive film blank at the temperature of 75 ℃ for 3h to obtain the transparent graphene conductive film. The aminating agent is ethylenediamine. The silver ammonia solution is prepared by mixing silver nitrate and water according to a mass ratio of 1: 30, and dropwise adding ammonia water with the mass fraction of 20% until all precipitates disappear to obtain a silver-ammonia solution.
Example 4
Mixing glucose and water according to a mass ratio of 1: 25, mixing the mixture in a beaker, adding potassium iodate with the mass 0.2 time that of glucose into the beaker, stirring and mixing the mixture for 60min at the temperature of 45 ℃ and the rotating speed of 400r/min to obtain a glucose mixed solution, mixing the glucose mixed solution with a barium chloride solution with the mass fraction of 18% according to the mass ratio of 1: 5, mixing, stirring and mixing for 50min at the temperature of 45 ℃ and the rotating speed of 400r/min, filtering to obtain a filtrate, and mixing the filtrate with a sodium sulfate solution with the mass fraction of 20% according to the mass ratio of 1: 4, mixing, stirring and mixing for 45min at the temperature of 45 ℃ and the rotating speed of 400r/min, filtering, and removing a filter cake to obtain a modified glucose mixture; mixing graphene oxide and water according to a mass ratio of 1: 300, performing ultrasonic dispersion for 30min under the condition that the frequency is 65kHz, adding an amination agent with the mass of 0.5 of graphene oxide into the mixture of the graphene oxide and water, and stirring and reacting for 10h under the conditions that the temperature is 60 ℃ and the rotating speed is 350r/min to obtain an aminated graphene oxide mixture; mixing polyallylamine hydrochloride and water according to a mass ratio of 1: 150, stirring and mixing for 40min at the temperature of 55 ℃ and the rotating speed of 400r/min, adjusting the pH value of a mixture of polyallylamine hydrochloride and water to 10.0 by using a sodium hydroxide solution with the mass fraction of 15% to obtain a polyallylamine hydrochloride solution, introducing nitrogen into the polyallylamine hydrochloride solution at the speed of 30mL/min, dripping a modified glucose mixture with the mass of 1.5 times that of the polyallylamine hydrochloride solution into the polyallylamine hydrochloride solution at the speed of 10mL/min under the rotating speed of 1200r/min, stirring and reacting for 4h at the temperature of 40 ℃ and the rotating speed of 400r/min to obtain a pretreatment additive blank, and mixing the pretreatment additive blank with sodium borohydride according to the mass ratio of 30: 1, mixing the mixture in a three-neck flask, introducing nitrogen into the three-neck flask at the rate of 30mL/min, stirring and reacting for 12 hours at the temperature of 65 ℃ and the rotating speed of 380r/min to obtain an additive blank, and dialyzing the additive blank for 20 hours by using a dialysis bag with the cut-off molecular weight of 10000 to obtain an additive; mixing an aminated graphene oxide mixture and a silver ammonia solution according to a mass ratio of 10: 1, mixing the mixture in a four-neck flask, adding an additive which is 0.2 times of the mass of the aminated graphene oxide mixture into the four-neck flask, and stirring and mixing for 50min under the conditions that the temperature is 55 ℃ and the rotating speed is 500r/min to obtain a mixture; introducing carbon dioxide into the mixture at a speed of 30mL/min, and stirring and mixing for 30min under the conditions that the temperature is 45 ℃ and the rotating speed is 300r/min to obtain a mixture; mixing the mixture with hydrazine hydrate according to the mass ratio of 10: 1, mixing, performing ultrasonic dispersion for 20min under the condition of 65kHz frequency, and stirring and reacting for 4h under the conditions of 55 ℃ and 450r/min of rotation speed to obtain blank liquid; and carrying out vacuum filtration on the blank liquid to obtain a transparent graphene conductive film blank, and drying the transparent graphene conductive film blank at the temperature of 75 ℃ for 3h to obtain the transparent graphene conductive film. The aminating agent is ethylenediamine. The silver ammonia solution is prepared by mixing silver nitrate and water according to a mass ratio of 1: 30, and dropwise adding ammonia water with the mass fraction of 20% until all precipitates disappear to obtain a silver-ammonia solution.
Comparative example: graphene conductive films produced by yowa science and technology limited.
The graphene conductive films obtained in examples 1 to 4 and comparative example products were subjected to performance testing, and the specific testing method was as follows:
the transmittance of the conductive film was measured by UV-Vis test, and the sheet resistance of the conductive film was measured by four probes.
Specific detection results are shown in table 1:
table 1: performance test meter
The detection results in table 1 show that the transparent graphene conductive film obtained by the invention has excellent conductive performance.
Claims (4)
1. A preparation method of a transparent graphene conductive film is characterized by comprising the following steps:
(1) mixing graphene oxide and water according to a mass ratio of 1: 200-1: 300, mixing, performing ultrasonic dispersion, adding an amination agent with the mass of 0.3-0.5 of graphene oxide, and stirring for reaction to obtain an aminated graphene oxide mixture;
(2) mixing polyallylamine hydrochloride and water according to a mass ratio of 1: 100-1: 150, adjusting the pH value to 9.8-10.0 to obtain a polyallylamine hydrochloride solution, introducing nitrogen into the polyallylamine hydrochloride solution, dripping a modified glucose mixture with the mass 1.0-1.5 times that of the polyallylamine hydrochloride solution into the polyallylamine hydrochloride solution under the condition of violent stirring to obtain a pretreatment additive blank after stirring reaction, and mixing the pretreatment additive blank with sodium borohydride according to the mass ratio of 20: 1-30: 1, mixing, stirring and mixing under the nitrogen atmosphere to obtain an additive blank, and dialyzing the additive blank to obtain an additive;
(3) mixing an aminated graphene oxide mixture and a silver ammonia solution according to a mass ratio of 5: 1-10: 1, adding an additive with the mass of 0.1-0.2 times of that of the aminated graphene oxide mixture and polyallylamine with the mass of 0.2-0.3 times of that of the aminated graphene oxide mixture, and stirring and mixing to obtain a polyallylamine mixture;
(4) introducing carbon dioxide into the polyallylamine mixture, and stirring and mixing to obtain a mixture; mixing the mixture with hydrazine hydrate according to a mass ratio of 8: 1-10: 1, mixing, ultrasonically dispersing, and stirring for reaction to obtain a blank liquid;
(5) and carrying out vacuum filtration on the blank liquid to obtain a transparent graphene conductive film blank, and drying the transparent graphene conductive film blank to obtain the transparent graphene conductive film.
2. The method according to claim 1, wherein the method comprises: the amination agent in the step (1) is any one of ethylenediamine, triethylene tetramine or diethylenetriamine.
3. The method according to claim 1, wherein the method comprises: the modified glucose mixture in the step (2) is prepared by mixing glucose and water according to the mass ratio of 1: 20-1: 25, adding potassium iodate with the mass being 0.1-0.2 times that of glucose, stirring and mixing to obtain a glucose mixed solution, mixing the glucose mixed solution with a barium chloride solution according to the mass ratio of 1: 3-1: 5, mixing and filtering to obtain a filtrate, and mixing the filtrate with a sodium sulfate solution according to a mass ratio of 1: 3-1: 4, mixing, filtering and removing filter cakes to obtain the modified glucose mixture.
4. The method according to claim 1, wherein the method comprises: and (3) preparing the silver ammonia solution by mixing silver nitrate and water according to the mass ratio of 1: 10-1: 30, and dropwise adding ammonia water until all precipitates disappear to obtain a silver-ammonia solution.
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