CN109337447B - Graphene quantum dot/nano silver wire composite water-based conductive ink and flexible transparent conductive film based on same - Google Patents
Graphene quantum dot/nano silver wire composite water-based conductive ink and flexible transparent conductive film based on same Download PDFInfo
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Abstract
The invention discloses graphene quantum dot/nano silver wire composite aqueous conductive ink and a flexible transparent conductive film based on the same: the conductive ink is prepared by uniformly mixing nano silver wires, graphene quantum dots, a dispersing film-forming aid and deionized water according to a certain proportion; the flexible transparent conductive film based on the graphene quantum dot/nano silver wire composite aqueous conductive ink is formed by coating the conductive layer on a flexible substrate, and the protective layer formed by coating the UV protective solution is formed on the conductive layer. The flexible transparent conductive film has the characteristics of good stability, low sheet resistance, excellent optical performance, simple preparation process and easiness in industrial production, and is suitable for large-size display and flexible display.
Description
Technical Field
The invention relates to the field of electronic display, in particular to graphene quantum dot/nano silver wire composite aqueous conductive ink and a flexible transparent conductive film prepared from the conductive ink.
Background
As consumer demand for large-sized display products and portable electronic products has increased, demand for flexible conductive films has increased in step. Currently, a conductive layer of a commercially available transparent conductive film is mainly Indium Tin Oxide (ITO), but the ITO film has the disadvantages of poor flexibility, high sheet resistance, expensive sputtering equipment and the like, and meanwhile, the ITO storage capacity is limited, and the price gradually rises with the increase of consumption.
In recent years, researchers have developed new technologies such as carbon nanotubes, graphene, silver nanowires, metal grids and the like to replace the ITO in succession, wherein the silver nanowires become the optimal alternative material for the ITO due to the characteristics of simple coating process, good optical performance, good electrical performance and the like. However, the nano silver wire conductive film mainly depends on nano silver wire network for conducting electricity, in order to achieve lower sheet resistance, the content of the nano silver wire must be increased, and the optical performance of the prepared conductive film can be influenced to a certain extent along with the increase of the content of the nano silver wire; meanwhile, the resistance value of the nano silver wire network node is a main factor for limiting the electrical performance of the conductive film, and when the nano silver wire network node is used in a flexible display screen, the resistance value change of the network node is also a main factor for influencing the reliability of the conductive film. Meanwhile, the nano silver wire has stronger activity and certain photo-thermal instability due to the nano size effect.
Therefore, in order to solve the existing problems of the silver nanowire transparent conductive film, the development of a flexible transparent conductive film with good stability, low sheet resistance and excellent optical performance is urgently needed.
Disclosure of Invention
In order to avoid the defects of the prior art, the invention aims to provide the flexible transparent conductive film with good stability, low sheet resistance and excellent optical performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention firstly discloses graphene quantum dot/nano silver wire composite aqueous conductive ink which is characterized by comprising the following raw materials in percentage by mass:
preferably, the diameter of the nano silver wire is 10-30nm, and the length-diameter ratio is 1000-1500.
Preferably, the thickness of the graphene quantum dot is less than or equal to 1nm, the sheet diameter of the graphene quantum dot is less than or equal to 10nm, and the surface of the graphene quantum dot contains one or more reactive functional groups of hydroxyl, carboxyl, carbonyl, imidazole and amino. The graphene quantum dots are commercially available graphene quantum dots meeting the size requirement, or are prepared by the following method: adding graphene oxide or graphene oxide quantum dots into water, performing ultrasonic dispersion uniformly to obtain an aqueous solution with the concentration of 5-20mg/mL, pouring the aqueous solution into a closed flask, treating the aqueous solution for 10-15h at 250 ℃ by using an oven, cooling and centrifuging, and drying the obtained precipitate to obtain the graphene quantum dots with the required size. The surfaces of the existing commercially available graphene oxide or graphene oxide quantum dots contain one or more reactive functional groups of hydroxyl, carboxyl, carbonyl, imidazole and amino, and after the graphene oxide or graphene oxide quantum dots are treated by the method, the surfaces of the obtained graphene quantum dots also contain corresponding functional groups. Meanwhile, the size of the existing commercially available graphene oxide or graphene oxide quantum dot is too large, and after the graphene oxide quantum dot is treated by the method, the obtained graphene quantum dot can be reduced to the required size, so that the graphene oxide quantum dot can effectively act on the node of the nano silver wire.
Preferably, the dispersing film-forming aid is one of methylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, carboxymethyl cellulose and polyvinylpyrrolidone or sodium polyacrylate.
Preferably, the TDS content of the deionized water is 0 ppm.
The invention relates to a preparation method of graphene quantum dot/nano silver wire composite conductive ink, which comprises the following steps:
a. sequentially adding deionized water and graphene quantum dots into a dispersion cylinder, and stirring at the speed of 500-; then slowly adding the nano silver wire into a dispersion cylinder, and continuously stirring for 30min to ensure that the graphene quantum dots are fully combined on the surface of the nano silver wire through coordination;
b. and slowly adding the dispersing film-forming assistant while continuously stirring, and then continuously stirring for 30min to prepare the graphene quantum dot/nano silver wire composite aqueous conductive ink.
The invention further discloses a flexible transparent conductive film based on the graphene quantum dot/nano silver wire composite aqueous conductive ink, which is characterized in that the flexible transparent conductive film is formed by coating the graphene quantum dot/nano silver wire composite aqueous conductive ink on a flexible substrate, and a protective layer formed by coating a UV protective solution is arranged on the conductive layer.
Preferably, the UV protection liquid comprises the following raw materials in percentage by mass:
preferably, the UV resin is one of AgiSyn 230a2, AgiSyn 2421, CN8011NS, CN8885NS and CN9010 NS; the photoinitiator is one of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxy-cyclohexyl benzophenone, diphenyl- (2,4, 6-trimethylbenzoyl) oxyphosphorus and benzoyl formate mixtures; the leveling agent is BYK-333; the solvent is prepared by compounding any three of acetone, cyclohexane, ethyl acetate, butanone, isopropanol, butyl acetate, isobutanol, cyclohexanone, carbon tetrachloride, chloroform, tetrahydrofuran, methyl acetate, ethylene glycol, 1, 3-propylene glycol, n-propanol, butanol and propyl ether according to the mass ratio of 1:1: 1.
The manufacturing method of the flexible transparent conductive film comprises the following steps:
a. coating the graphene quantum dot/nano silver wire composite aqueous conductive ink on a flexible substrate through a micro-concave coating process, and then drying for 1-2min at 100 ℃ through a tunnel furnace to form a conductive layer;
b. coating UV protective solution on the surface of the conductive layer by a micro-concave coating process, and then coating the surface of the conductive layer at 500mJ/cm2Energy UV curing is carried out for 5-10s to form a protective layer, and the flexible transparent conductive film is prepared;
c. and covering a high-temperature-resistant PET protective film on the surface of the protective layer of the flexible transparent conductive film, and rolling.
Preferably, the flexible substrate is polyethylene terephthalate (PET) or Polyimide (PI).
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, through reasonable configuration of a formula system, all raw materials in the system act synergistically, and the transparent conductive film prepared by the conductive ink has high stability, low sheet resistance and excellent optical performance.
2. The invention adopts graphene quantum dots, and the action mechanism of the graphene quantum dots is represented as follows: the surface of the graphene quantum dot contains reactive functional groups, so that the graphene quantum dot has excellent dispersing performance in a plurality of solvents and water, and is convenient to add in the composite conductive ink; the graphene quantum dots are small in size and have an electron-rich characteristic, and can be combined with the nano silver wire with an electrophilic characteristic through a coordination effect, so that the surface of the nano silver wire is coated with a large number of graphene quantum dots, the reaction of the nano silver wire with air and water is prevented, and the photo-thermal stability of the nano silver wire is improved; because the electrophilic performance at the nano-silver wire node is excellent, the coordination effect of the graphene quantum dot and the nano-silver wire is more obvious, the nano-silver wire contact resistance is reduced while the nano-silver wire is well fixed at the node, so that the sheet resistance of the conductive film is reduced, the nano-silver wire content required by the conductive film with the same sheet resistance is lower, and the optical performance of the obtained conductive film is more excellent; the graphene quantum dots can be bonded with the surface of the substrate or a dispersing film-forming auxiliary agent in the conductive ink through hydrogen bonds or chemical bonds due to the reactive groups contained on the surface, so that the adhesive force and the bending resistance of the conductive film are improved;
3. the invention has simple process, can be coated roll to roll and is easy to realize industrial production.
Detailed Description
The present invention will be described in detail with reference to the following examples, which are carried out on the premise of the technical solution of the present invention, and give detailed embodiments and specific procedures, but the scope of the present invention is not limited to the following examples.
The formulations of the UV protection solutions used in the following comparative and examples are as follows:
the preparation method comprises the following steps: adding UV resin CN9010NS, a photoinitiator 1173, a flatting agent BYK-333 and a solvent (prepared by compounding butanone, ethyl acetate and ethylene glycol according to the mass ratio of 1:1: 1) into a dispersion cylinder in sequence, and stirring for 60min at the speed of 500r/min by using a tetrafluoroethylene stirring rod to prepare the UV protection solution.
Comparative example 1
(1) Preparing the aqueous conductive ink:
the water-based conductive ink of the comparative example comprises the following raw materials in percentage by mass:
0.1% of nano silver wire;
0.2% of dispersing film-forming assistant;
and 99.7% of deionized water.
Wherein: the diameter of the used nano silver wire is 10-15nm, and the length-diameter ratio is 1300-1500; the dispersing film-forming assistant is hydroxyethyl cellulose; the TDS content of the deionized water used was 0 ppm.
The preparation method comprises the following steps: sequentially adding the dispersing film-forming assistant and deionized water into a dispersing cylinder, and stirring at the speed of 500r/min for 30min to prepare a uniform solution; and slowly adding the nano silver wire, and continuously stirring for 30min to obtain the water-based conductive ink.
(2) Preparing a flexible transparent conductive film:
a. coating the aqueous conductive ink prepared in the step (1) on a PET (polyethylene terephthalate) non-hardened surface through a micro-concave coating process, and then drying by using a tunnel furnace (100 ℃, 1min) to prepare a conductive layer;
b. coating UV protective solution on the surface of the conductive layer by a micro-concave coating process, and then UV curing (500 mJ/cm)2And 10s) forming a protective layer to obtain the flexible transparent conductive film.
c. Covering a high-temperature-resistant PET protective film on the surface of the protective layer of the flexible transparent conductive film prepared in the step (b), rolling and warehousing for later use.
Comparative example 2
(1) Preparing the aqueous conductive ink:
the water-based conductive ink of the comparative example comprises the following raw materials in percentage by mass:
0.13% of nano silver wire;
0.2% of dispersing film-forming assistant;
and 99.67 percent of deionized water.
Wherein: the diameter of the used nano silver wire is 10-15nm, and the length-diameter ratio is 1300-1500; the dispersing film-forming assistant is hydroxyethyl cellulose; the TDS content of the deionized water used was 0 ppm.
The preparation method comprises the following steps: sequentially adding the dispersing film-forming assistant and deionized water into a dispersing cylinder, and stirring at the speed of 500r/min for 30min to prepare a uniform solution; and slowly adding the nano silver wire, and continuously stirring for 30min to obtain the water-based conductive ink.
(2) Preparing a flexible transparent conductive film:
a. coating the aqueous conductive ink prepared in the step (1) on a PET (polyethylene terephthalate) non-hardened surface through a micro-concave coating process, and then drying by using a tunnel furnace (100 ℃, 1min) to prepare a conductive layer;
b. coating UV protective solution on the surface of the conductive layer by a micro-concave coating process, and then UV curing (500 mJ/cm)2And 10s) forming a protective layer to obtain the flexible transparent conductive film.
c. Covering a high-temperature-resistant PET protective film on the surface of the protective layer of the flexible transparent conductive film prepared in the step (b), rolling and warehousing for later use.
Example 1
(1) Preparing graphene quantum dot/nano silver wire composite aqueous conductive ink:
the graphene quantum dot/nano silver wire composite aqueous conductive ink comprises the following raw materials in percentage by mass:
the preparation method comprises the following steps: sequentially adding deionized water and graphene quantum dots into a dispersion cylinder, and stirring at the speed of 500r/min for 30min to prepare a uniform solution; then slowly adding the nano silver wire into the solution, and continuously stirring for 30min to ensure that the graphene quantum dots are fully combined on the surface of the nano silver wire through coordination; and slowly adding the dispersing film-forming assistant, and continuously stirring for 30min to obtain the graphene quantum dot/nano silver wire composite aqueous conductive ink.
Wherein: the diameter of the used nano silver wire is 10-15nm, and the length-diameter ratio is 1300-1500; the used graphene quantum dots are JCGOD-0.6-4-W (the thickness is 0.33-1nm, the sheet diameter is 3-6nm, and the size is Jicann nanometer); the dispersing film-forming assistant is hydroxyethyl cellulose; the TDS content of the deionized water used was 0 ppm.
(2) Preparing a flexible transparent conductive film:
a. coating the aqueous conductive ink prepared in the step (1) on a PET (polyethylene terephthalate) non-hardened surface through a micro-concave coating process, and then drying by using a tunnel furnace (100 ℃, 1min) to prepare a conductive layer;
b. coating UV protective solution on the surface of the conductive layer by a micro-concave coating process, and then UV curing (500 mJ/cm)210s) forming a protective layer to obtain a target flexible transparent conductive film;
c. covering the surface of the flexible transparent conductive film protective layer prepared in the step (b) with a high-temperature-resistant PET protective film, rolling and warehousing for later use.
Example 2
(1) Preparing graphene quantum dot/nano silver wire composite aqueous conductive ink:
the graphene quantum dot/nano silver wire composite aqueous conductive ink comprises the following raw materials in percentage by mass:
the preparation method comprises the following steps:
a. adding the graphene oxide quantum dots into water, performing ultrasonic dispersion uniformly to obtain an aqueous solution of the graphene oxide quantum dots with the concentration of 10mg/mL, pouring the aqueous solution into a closed flask, treating the aqueous solution for 10 hours at 200 ℃ by using an oven, cooling and centrifuging, and drying the obtained precipitate to obtain the graphene quantum dots with the thickness of less than or equal to 1nm and the sheet diameter of less than or equal to 10 nm.
b. Sequentially adding deionized water and graphene quantum dots into a dispersion cylinder, and stirring at the speed of 500r/min for 30min to prepare a uniform solution; then slowly adding the nano silver wire into the solution, and continuously stirring for 30min to ensure that the graphene quantum dots are fully combined on the surface of the nano silver wire through coordination; and slowly adding the dispersing film-forming assistant, and continuously stirring for 30min to obtain the graphene quantum dot/nano silver wire composite aqueous conductive ink.
Wherein: the diameter of the used nano silver wire is 10-15nm, and the length-diameter ratio is 1300-1500; the used graphene oxide quantum dots are XF074 (thickness is 1-2nm, sheet diameter is 5-15nm, and the size is Feng nanometer); the dispersing film-forming assistant is hydroxyethyl cellulose; the TDS content of the deionized water used was 0 ppm.
(2) Preparing a flexible transparent conductive film:
a. coating the aqueous conductive ink prepared in the step (1) on a PET (polyethylene terephthalate) non-hardened surface through a micro-concave coating process, and then drying by using a tunnel furnace (100 ℃, 1min) to prepare a conductive layer;
b. coating UV protective solution on the surface of the conductive layer by a micro-concave coating process, and then UV curing (500 mJ/cm)210s) forming a protective layer to obtain a target flexible transparent conductive film;
c. covering the surface of the flexible transparent conductive film protective layer prepared in the step (b) with a high-temperature-resistant PET protective film, rolling and warehousing for later use.
Example 3
(1) Preparing graphene quantum dot/nano silver wire composite aqueous conductive ink:
the graphene quantum dot/nano silver wire composite aqueous conductive ink comprises the following raw materials in percentage by mass:
the preparation method comprises the following steps:
a. adding graphene oxide into water, performing ultrasonic dispersion uniformly to obtain a graphene oxide aqueous solution with the concentration of 10mg/mL, pouring the graphene oxide aqueous solution into a closed flask, processing the graphene oxide aqueous solution for 15 hours at 210 ℃ by using an oven, then cooling and centrifuging, and drying the obtained precipitate to obtain the graphene quantum dots with the thickness of less than or equal to 1nm and the sheet diameter of less than or equal to 10 nm.
b. Sequentially adding deionized water and graphene quantum dots into a dispersion cylinder, and stirring at the speed of 500r/min for 30min to prepare a uniform solution; then slowly adding the nano silver wire into the solution, and continuously stirring for 30min to ensure that the graphene quantum dots are fully combined on the surface of the nano silver wire through coordination; and slowly adding the dispersing film-forming assistant, and continuously stirring for 30min to obtain the graphene quantum dot/nano silver wire composite aqueous conductive ink.
Wherein: the diameter of the used nano silver wire is 10-15nm, and the length-diameter ratio is 1300-1500; the used graphene oxide is XF004L (thickness is 0.8-1.2nm, sheet diameter is 0.5-5 μm, and the size is Feng nanometer); the dispersing film-forming assistant is hydroxyethyl cellulose; the TDS content of the deionized water used was 0 ppm.
(2) Preparing a flexible transparent conductive film:
a. coating the aqueous conductive ink prepared in the step (1) on a PET (polyethylene terephthalate) non-hardened surface through a micro-concave coating process, and then drying by using a tunnel furnace (100 ℃, 1min) to prepare a conductive layer;
b. coating UV protective solution on the surface of the conductive layer by a micro-concave coating process, and then UV curing (500 mJ/cm)210s) forming a protective layer to obtain a target flexible transparent conductive film;
c. covering the surface of the flexible transparent conductive film protective layer prepared in the step (b) with a high-temperature-resistant PET protective film, rolling and warehousing for later use.
Example 4
(1) Preparing graphene quantum dot/nano silver wire composite aqueous conductive ink:
the graphene quantum dot/nano silver wire composite aqueous conductive ink comprises the following raw materials in percentage by mass:
the preparation method comprises the following steps:
a. adding the graphene oxide quantum dots into water, performing ultrasonic dispersion uniformly to obtain an aqueous solution of the graphene oxide quantum dots with the concentration of 10mg/mL, pouring the aqueous solution into a closed flask, treating the aqueous solution for 10 hours at 200 ℃ by using an oven, cooling and centrifuging, and drying the obtained precipitate to obtain the graphene quantum dots with the thickness of less than or equal to 1nm and the sheet diameter of less than or equal to 10 nm.
b. Sequentially adding deionized water and graphene quantum dots into a dispersion cylinder, and stirring at the speed of 500r/min for 30min to prepare a uniform solution; then slowly adding the nano silver wire into the solution, and continuously stirring for 30min to ensure that the graphene quantum dots are fully combined on the surface of the nano silver wire through coordination; and slowly adding the dispersing film-forming assistant, and continuously stirring for 30min to obtain the graphene quantum dot/nano silver wire composite aqueous conductive ink.
Wherein: the diameter of the used nano silver wire is 10-15nm, and the length-diameter ratio is 1300-1500; the used graphene oxide quantum dots are XF074 (thickness is 1-2nm, sheet diameter is 5-15nm, and the size is Feng nanometer); the dispersing film-forming assistant is hydroxyethyl cellulose; the TDS content of the deionized water used was 0 ppm.
(2) Preparing a flexible transparent conductive film:
a. coating the aqueous conductive ink prepared in the step (1) on a PET (polyethylene terephthalate) non-hardened surface through a micro-concave coating process, and then drying by using a tunnel furnace (100 ℃, 1min) to prepare a conductive layer;
b. coating UV protective solution on the surface of the conductive layer by a micro-concave coating process, and then UV curing (500 mJ/cm)210s) forming a protective layer to obtain a target flexible transparent conductive film;
c. covering the surface of the flexible transparent conductive film protective layer prepared in the step (b) with a high-temperature-resistant PET protective film, rolling and warehousing for later use.
Example 5
(1) Preparing graphene quantum dot/nano silver wire composite aqueous conductive ink:
the graphene quantum dot/nano silver wire composite aqueous conductive ink comprises the following raw materials in percentage by mass:
the preparation method comprises the following steps:
a. adding the graphene oxide quantum dots into water, performing ultrasonic dispersion uniformly to obtain an aqueous solution of the graphene oxide quantum dots with the concentration of 10mg/mL, pouring the aqueous solution into a closed flask, treating the aqueous solution for 10 hours at 200 ℃ by using an oven, cooling and centrifuging, and drying the obtained precipitate to obtain the graphene quantum dots with the thickness of less than or equal to 1nm and the sheet diameter of less than or equal to 10 nm.
b. Sequentially adding deionized water and graphene quantum dots into a dispersion cylinder, and stirring at the speed of 500r/min for 30min to prepare a uniform solution; then slowly adding the nano silver wire into the solution, and continuously stirring for 30min to ensure that the graphene quantum dots are fully combined on the surface of the nano silver wire through coordination; and slowly adding the dispersing film-forming assistant, and continuously stirring for 30min to obtain the graphene quantum dot/nano silver wire composite aqueous conductive ink.
Wherein: the diameter of the used nano silver wire is 10-15nm, and the length-diameter ratio is 1300-1500; the used graphene oxide quantum dots are XF074 (thickness is 1-2nm, sheet diameter is 5-15nm, and the size is Feng nanometer); the dispersing film-forming assistant is hydroxyethyl cellulose; the TDS content of the deionized water used was 0 ppm.
(2) Preparing a flexible transparent conductive film:
a. coating the aqueous conductive ink prepared in the step (1) on a PET (polyethylene terephthalate) non-hardened surface through a micro-concave coating process, and then drying by using a tunnel furnace (100 ℃, 1min) to prepare a conductive layer;
b. coating UV protective solution on the surface of the conductive layer by a micro-concave coating process, and then UV curing (500 mJ/cm)210s) forming a protective layer to obtain a target flexible transparent conductive film;
c. covering the surface of the flexible transparent conductive film protective layer prepared in the step (b) with a high-temperature-resistant PET protective film, rolling and warehousing for later use.
Table 1: comparison of Performance between comparative example 1 and examples 1-3
From the comparison result between the comparative example 1 and the examples 1 to 3, the sheet resistance of the conductive film can be effectively reduced by the graphene quantum dots with required sizes, which are prepared by adding different types of graphene oxides or graphene oxide quantum dots into the conductive ink, and the prepared graphene quantum dots play a good role in connection and fixation at the nano-silver network nodes; moreover, the light transmittance of the graphene quantum dots is larger than 98%, and the addition amount is very low, so that the optical properties (haze and light transmittance) of the conductive film after the graphene quantum dots are added are not obviously changed under the condition that the content of the nano silver wires is the same; meanwhile, the bending resistance radius of the conductive film is obviously reduced, and the weather resistance (UV aging, xenon lamp aging, high temperature and high humidity) is obviously improved.
Table 2: EXAMPLES 2 AND 4-5 Performance alignment
From the comparison results of the embodiment 2 and the embodiments 4 to 5, it can be seen that as the content of the graphene quantum dots in the conductive ink is gradually increased: (1) the optical properties (haze and light transmittance) of the prepared conductive film are not obviously changed, which shows that the influence of the addition of the graphene quantum dots on the optical properties of the conductive film is extremely low; (2) the sheet resistance of the prepared conductive film is continuously reduced, but the reduction trend is gradually weakened; (3) the bending resistance radius of the prepared conductive film is continuously reduced, the weather resistance (UV aging, xenon lamp aging, high temperature and high humidity) is continuously improved, but when the content of the graphene quantum dots is improved to a certain degree, the content of the graphene quantum dots is continuously improved, and the improvement effect is not obvious; probably, as the graphene quantum dots are improved, the adsorption on the surface of the nano silver wire and the adsorption and fixation at the nodes tend to be saturated, and no obvious effect is achieved when the graphene quantum dots are continuously improved.
Table 3: comparison of comparative examples 1-2 with example 2
From the comparison results of the comparative examples 1-2 and the example 2, when the graphene quantum dots are not added in the conductive ink, the conductive film prepared by the silver nanowires with higher concentration can reach a certain sheet resistance, but the increase of the content of the silver nanowires has a certain influence on the optical performance (haze and light transmittance) of the conductive film; after the graphene quantum dots are added into the conductive ink, the conductive film with the same sheet resistance can be obtained under the condition of lower nano silver wire content, and the optical performance is more excellent.
The present invention is not limited to the above exemplary embodiments, and any modifications, equivalent replacements, and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The graphene quantum dot/nano silver wire composite aqueous conductive ink is characterized by comprising the following raw materials in percentage by mass:
the thickness of the graphene quantum dots is less than or equal to 1nm, and the sheet diameter is less than or equal to 10 nm; the surface of the graphene quantum dot contains one or more reactive functional groups of hydroxyl, carboxyl, carbonyl, imidazole and amino;
the diameter of the nano silver wire is 10-30nm, and the length-diameter ratio is 1000-1500;
the preparation method of the graphene quantum dot/nano silver wire composite aqueous conductive ink comprises the following steps:
a. sequentially adding deionized water and graphene quantum dots into a dispersion cylinder, and stirring at the speed of 500-; then slowly adding the nano silver wire into a dispersion cylinder, and continuously stirring for 30min to ensure that the graphene quantum dots are fully combined on the surface of the nano silver wire through coordination;
b. and slowly adding the dispersing film-forming assistant while continuously stirring, and then continuously stirring for 30min to prepare the graphene quantum dot/nano silver wire composite aqueous conductive ink.
2. The graphene quantum dot/nano silver wire composite aqueous conductive ink according to claim 1, wherein: the dispersing film-forming auxiliary agent is one of methyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, polyvinylpyrrolidone and sodium polyacrylate; the TDS content of the deionized water was 0 ppm.
3. The graphene quantum dot/nano silver wire composite aqueous conductive ink according to claim 1, wherein the graphene quantum dot is a commercially available graphene quantum dot meeting size requirements, or is prepared by the following method: adding graphene oxide or graphene oxide quantum dots into water, performing ultrasonic dispersion uniformly to obtain an aqueous solution with the concentration of 5-20mg/mL, pouring the aqueous solution into a closed flask, treating the aqueous solution for 10-15h at 250 ℃ by using an oven, cooling and centrifuging, and drying the obtained precipitate to obtain the graphene quantum dots with the required size.
4. A flexible transparent conductive film based on the graphene quantum dot/nano silver wire composite aqueous conductive ink as claimed in any one of claims 1 to 3, characterized in that: the flexible transparent conductive film is formed by coating the graphene quantum dot/nano silver wire composite aqueous conductive ink on a flexible substrate, and a protective layer formed by coating a UV protective solution is arranged on the conductive layer.
5. The flexible transparent conductive film of claim 4, wherein: the UV protection solution is prepared by uniformly mixing the following raw materials in percentage by mass:
6. the flexible transparent conductive film of claim 5, wherein: the UV resin is one of AgiSyn 230A2, AgiSyn 2421, CN8011NS, CN8885NS and CN9010 NS; the photoinitiator is one of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxy-cyclohexyl benzophenone, diphenyl- (2,4, 6-trimethylbenzoyl) oxyphosphorus and benzoyl formate mixtures; the leveling agent is BYK-333; the solvent is prepared by compounding any three of acetone, cyclohexane, ethyl acetate, butanone, isopropanol, butyl acetate, isobutanol, cyclohexanone, carbon tetrachloride, chloroform, tetrahydrofuran, methyl acetate, ethylene glycol, 1, 3-propylene glycol, n-propanol, butanol and propyl ether according to the mass ratio of 1:1: 1.
7. A method for manufacturing a flexible transparent conductive film according to any one of claims 4 to 6, comprising the steps of:
a. coating the graphene quantum dot/nano silver wire composite aqueous conductive ink on a flexible substrate through a micro-concave coating process, and then drying for 1-2min at 100 ℃ through a tunnel furnace to form a conductive layer;
b. coating UV protective solution on the surface of the conductive layer by a micro-concave coating process, and then coating the surface of the conductive layer at 500mJ/cm2Energy UV curing is carried out for 5-10s to form a protective layer, and the flexible transparent conductive film is prepared;
c. and covering a high-temperature-resistant PET protective film on the surface of the protective layer of the flexible transparent conductive film, and rolling.
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