CN112201390A - Flexible composite transparent conductive film and preparation method thereof - Google Patents
Flexible composite transparent conductive film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a flexible composite transparent conductive film, which comprises a polyethylene glycol terephthalate substrate layer, a blending layer of nano-cellulose and silver nanowires and a graphene oxide layer which are sequentially contacted, wherein the nano-cellulose has a three-dimensional network porous structure and is used as a support material for bearing the silver nanowires, so that the silver nanowires are spread on the surface of the nano-cellulose and are uniformly dispersed, the agglomeration phenomenon of the silver nanowires is reduced, and the silver nanowires have good film-forming property and smooth and uniform surface.
Description
Technical Field
The invention relates to the technical field of photoelectricity, in particular to a flexible composite transparent conductive film and a preparation method thereof.
Background
In recent years, with the rapid development of flexible photoelectric devices, flexible transparent conductive films have been widely used in the fields of touch screens, sensors, solar cells, transparent heaters, and the like. Currently, Indium Tin Oxide (ITO) has been widely used as an oxide conductor for preparing an electrode material of a photoelectric device, and has many advantages such as high stability in an atmosphere, high light transmittance, and the like. However, with the development of flexible electronic devices, the conventional ITO transparent conductive film also has exposed more and more disadvantages, such as brittleness, shortage of indium resources, high cost, and the like. Therefore, a need for a material capable of replacing ITO is imminent, in which graphene, carbon nanotubes, conductive polymers, and silver nanowires are all conductive materials with excellent performance, and can be considered as candidates.
Compared with other conductive materials, the silver nanowire transparent conductive film gradually enters the visual field of people due to the advantages of excellent flexibility, low preparation cost, simple operation process and the like. However, the bottleneck problem limiting the practical application of the silver nanowire transparent conductive film is also obvious, for example, in a flexible substrate silver nanowire transparent conductive film with the publication number of CN201910557389.2 and a preparation method thereof, a silver nanowire ethanol dispersion liquid is sprayed on a rigid substrate, and the silver nanowire transparent conductive film is dried and cured, so that the cohesiveness among silver nanowires can be effectively improved, and the conductivity and uniformity of the silver nanowire network can be greatly improved. Meanwhile, the problems of weak connection between the silver nanowires and PDMS and poor robustness of the transparent conductive film can be solved due to the introduction of the colorless and transparent light-cured adhesive; the driving voltage of the electrochromic device can be reduced. Although the method can realize strong connection between the silver nanowires and the flexible substrate, can improve the robustness of the silver nanowire transparent conductive film and reduce the junction resistance between the silver nanowires, the prepared silver nanowire transparent conductive film has low light transmittance, large surface roughness and easy oxidation.
Disclosure of Invention
In order to solve the problems, the invention provides a flexible composite transparent conductive film and a preparation method thereof, which have the advantages of high light transmission, oxidation resistance, good film forming property and uniformity.
The technical scheme for solving the problem is that the flexible composite transparent conductive film comprises a polyethylene terephthalate substrate layer, a blending layer of nano-cellulose and silver nanowires and a graphene oxide layer which are sequentially contacted.
Preferably, the molar ratio of the silver nanowires to the nanocellulose is 1: 1-3, and the proper molar ratio is selected, so that any material is not excessive.
Also provides a preparation method of the flexible composite transparent conductive film, which comprises the following steps:
K1. pretreating the surface of the substrate to obtain a pretreated substrate surface;
K2. coating the blended solution of the silver nanowires and the nanocellulose on the surface of the pretreated substrate, and then carrying out heat treatment to obtain a composite substrate;
K3. and coating uniformly dispersed graphene oxide solution on the surface of the composite substrate, and then carrying out heat treatment to obtain the flexible composite transparent conductive film.
Preferably, the specific operation of pretreatment in the K1 step comprises ultrasonic cleaning with acetone or isopropyl alcohol and then irradiating with ultraviolet-ozone.
Preferably, the concentration of the silver nanowire solution is 1-5mg/ml, and the solvent in the scheme is water.
Preferably, the concentration of the nano-cellulose solution is 0.5-2.5% so as to match the concentration of the silver nanowires.
Preferably, the concentration of the graphene oxide solution is 1-5mg/ml, waste is caused by too high concentration, and the utilization rate of the silver nanowires is low when the concentration is too low.
Preferably, the coating spin speed is 1000-.
Preferably, the heat treatment temperature is 80-150 ℃, the heat treatment time is 5-20 min, the reaction condition is mild, the film forming property is good and uniform, the environmental stability is good, and the film can be stretched, bent and recovered.
Preferably, the heat treatment temperature in the step K3 is 80-100 ℃, the heat treatment time is 5-10 min, the use temperature and the heat treatment time of the graphene oxide are further limited, and the instability of the graphene oxide caused by overhigh heat treatment temperature or overlong heat treatment time of the graphene oxide is avoided.
In the scheme, graphene oxide and nano-cellulose materials are introduced to modify silver nanowires together to prepare the composite flexible transparent conductive film. The nano-cellulose is used as a novel green nano-material, is rich in reserve and can be recycled; the nano-silver film has a three-dimensional network porous structure, can be used as a support material to bear the nano-silver wires, so that the nano-silver wires are spread on the surface of the nano-cellulose and are uniformly dispersed, and the property of the nano-silver film is improved; the nano-cellulose has excellent planarity and good light transmittance, and can effectively improve the light transmittance of the silver nanowires when being mixed with the silver nanowires; the nano-cellulose has good gas barrier property, can weaken the oxidation of the silver nanowires in air when being mixed with the silver nanowires, and simultaneously has certain conductivity due to the porous structure. The graphene oxide material has good light transmittance and certain flexibility, an excellent planar structure is endowed with a unique sp2 hybrid structure, and the graphene oxide material is enabled to be micro-wavy due to oxygen-containing groups, so that the contact area is increased, and the functions of the graphene oxide material are effectively exerted; the blending layer of the nano-cellulose and the silver nanowires is coated with a layer of graphene oxide, so that the light transmittance of the film can be improved, and the film can also be used as a protective film to improve the oxidation resistance of the film. The flexible transparent conductive film prepared by the solution method has excellent conductivity and light transmittance, good and uniform film forming property, good environmental stability, and can be stretched, bent and recovered.
The flexible transparent conductive film prepared by the invention has excellent conductivity (10 omega/sq), good light transmittance (90%), good film forming property (smooth and uniform surface and weakened silver nanowire agglomeration phenomenon), excellent flexibility (can be stretched and bent in different directions and can be recovered to an original shape), mechanical stability (the recovery resistance value is not changed greatly after 200 bending and stretching operations), and environmental stability (the resistance value is not changed greatly after 1 month).
The invention has the beneficial effects that:
1. the nano-cellulose has a three-dimensional network porous structure and is used as a support material for bearing the silver nanowires, so that the silver nanowires are spread on the surface of the nano-cellulose, are uniformly dispersed, the agglomeration phenomenon of the silver nanowires is reduced, the silver nanowires have good film-forming property, and the surface is smooth and uniform;
2. the nano-cellulose has excellent planarity and good light transmittance, and can effectively improve the light transmittance of the silver nanowires when being mixed with the silver nanowires;
3. the nano-cellulose has good gas barrier property, can weaken the oxidation of the silver nanowires in air when being mixed with the silver nanowires, and simultaneously ensures that the mixed solution has certain conductivity due to a porous structure;
4. the graphene oxide material has good light transmittance and certain flexibility, the unique sp2 hybrid structure endows the graphene oxide material with an excellent planar structure, and the oxygen-containing groups enable the graphene oxide material to be in a micro-wave shape, so that the contact area is increased, the prepared flexible transparent conductive film can be stretched and bent in different directions and can be restored to the original shape, and the mechanical stability is high.
5. The blending layer of the nano-cellulose and the silver nanowires is coated with a layer of graphene oxide, so that the light transmittance of the film can be improved, and the graphene oxide can also be used as a protective film to improve the oxidation resistance of the film.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
The flexible transparent conductive film is mainly prepared on polyethylene terephthalate (PET) by spin coating. The method comprises the following specific steps:
(1) and (3) taking 20 mg/ml silver nanowire raw solution, diluting to 1mg/ml, and placing in a reagent bottle.
(2) Taking 2.5 +/-0.5% of nano-cellulose solution, diluting to 0.5%, and placing in a reagent bottle.
(3) Preparing a graphene oxide solution with the concentration of 1mg/ml, and carrying out ultrasonic treatment for 10 hours to ensure uniform dispersion.
(4) Uniformly mixing the appropriate amount of the solution in the step (1) and the solution in the step (2), wherein the mixing ratio is 1: 1, placing the mixture in a reagent bottle for standby use.
(5) Cutting 1.5X 1.5 cm2And marking.
(6) Placing the PET substrate in the step (5) on dust-free cloth, cleaning the surface of the PET substrate with cleaning liquid, then placing the PET substrate into a beaker with a polytetrafluoroethylene cleaning rack, respectively pouring acetone and isopropanol, cleaning the PET substrate for 10 min under the ultrasonic condition, drying the PET substrate by blowing, and then placing the PET substrate into a UV-O (ultraviolet-oxygen) device3Performing ultraviolet-ozone treatment in an irradiation machine for 10 min.
(7) And (3) preheating the heat treatment machine to a specified temperature, taking the prepared solutions in the steps (3) and (4) and the treated substrate in the step (5), and carrying out spin coating to prepare the flexible transparent conductive film. Firstly, cleaning the surface of a substrate by using a spray gun (the surface of the substrate is contacted with the atmosphere when the substrate is taken out of an irradiation machine and placed in a culture dish, and some dust is inevitably generated, the substrate is blown off by using the spray gun), then, carrying out spin coating, heat treatment, graphene oxide solution spin coating and heat treatment on the substrate in sequence, wherein the spin coating speed is controlled at 1000 rpm, the spin coating time is controlled at 30 s, the spin coating acceleration is 100 rpm/s, the heat treatment temperature of the blend solution coated with the nano-cellulose and the silver nano-wires and the heat treatment temperature of the graphene oxide solution coated are both controlled at 80 ℃, and the heat treatment time is controlled at 5 min, thus obtaining the flexible composite transparent conductive film.
Example 2
The flexible transparent conductive film is mainly prepared on polyethylene terephthalate (PET) by spin coating. The method comprises the following specific steps:
(1) and (3) taking 20 mg/ml silver nanowire raw solution, diluting to 5mg/ml, and placing in a reagent bottle.
(2) Taking 2.5 +/-0.5% of nano-cellulose solution, diluting to 2.5%, and placing in a reagent bottle.
(3) Preparing 5mg/ml graphene oxide solution, and carrying out ultrasonic treatment for 10 hours to ensure uniform dispersion.
(4) Uniformly mixing the appropriate amount of the solution in the step (1) and the solution in the step (2), wherein the mixing ratio is 1: and 2, placing the reagent bottle for standby use.
(5) Cutting 1.5X 1.5 cm2And marking.
(6) Placing the PET substrate in the step (5) on dust-free cloth, cleaning the surface of the PET substrate with cleaning liquid, then placing the PET substrate into a beaker with a polytetrafluoroethylene cleaning rack, respectively pouring acetone and isopropanol, cleaning the PET substrate for 10 min under the ultrasonic condition, drying the PET substrate by blowing, and then placing the PET substrate into a UV-O (ultraviolet-oxygen) device3Performing ultraviolet-ozone treatment in an irradiation machine for 10 min.
(7) And (3) preheating the heat treatment machine to a specified temperature, taking the prepared solutions in the steps (3) and (4) and the treated substrate in the step (5), and carrying out spin coating to prepare the flexible transparent conductive film. Firstly, cleaning the surface of a substrate by using a spray gun (the surface of the substrate is contacted with the atmosphere when the substrate is taken out of an irradiation machine and placed in a culture dish, and some dust is inevitably generated and blown off by using the spray gun), then sequentially carrying out blended solution spin coating-heat treatment-graphene oxide solution spin coating-heat treatment on the substrate, wherein the spin coating speed is controlled at 4000rpm, the spin coating time is controlled at 60s, the spin coating acceleration is 200 rpm/s, the temperature of the blended solution for coating the nano-cellulose and the silver nanowires is controlled at 150 ℃, the heat treatment time is controlled at 20 min, the heat treatment temperature for coating the graphene oxide solution is controlled at 90 ℃, the heat treatment time is controlled at 8 min, and the flexible composite transparent conductive film is obtained by coating.
Example 3
The flexible transparent conductive film is mainly prepared on polyethylene terephthalate (PET) by spin coating. The method comprises the following specific steps:
(1) and (3) taking 20 mg/ml silver nanowire raw solution, diluting to 2 mg/ml, and placing in a reagent bottle.
(2) Taking 2.5 +/-0.5% of nano-cellulose solution, diluting to 1%, and placing in a reagent bottle.
(3) Preparing a graphene oxide solution with the concentration of 3 mg/ml, and carrying out ultrasonic treatment for 10 hours to ensure uniform dispersion.
(4) Uniformly mixing the appropriate amount of the solution in the step (1) and the solution in the step (2), wherein the mixing ratio is 1: and 3, placing the mixture in a reagent bottle for standby use.
(5) Cutting 1.5X 1.5 cm2And marking.
(6) Placing the PET substrate in the step (5) on dust-free cloth, cleaning the surface of the PET substrate with cleaning liquid, then placing the PET substrate into a beaker with a polytetrafluoroethylene cleaning rack, respectively pouring acetone and isopropanol, cleaning the PET substrate for 10 min under the ultrasonic condition, drying the PET substrate by blowing, and then placing the PET substrate into a UV-O (ultraviolet-oxygen) device3Performing ultraviolet-ozone treatment in an irradiation machine for 10 min.
(7) And (3) preheating the heat treatment machine to a specified temperature, taking the prepared solutions in the steps (3) and (4) and the treated substrate in the step (5), and carrying out spin coating to prepare the flexible transparent conductive film. Firstly, cleaning the surface of a substrate by using a spray gun (the surface of the substrate is contacted with the atmosphere when the substrate is taken out of an irradiation machine and placed in a culture dish, and some dust is inevitably generated, the substrate is blown off by using the spray gun), then, carrying out spin coating, heat treatment, graphene oxide solution spin coating and heat treatment on the substrate in sequence, wherein the spin coating speed is controlled at 2000 rpm, the spin coating time is controlled at 50 s, the spin coating acceleration is 150 rpm/s, the heat treatment temperature of the blend solution coated with the nano-cellulose and the silver nanowires and the heat treatment temperature of the graphene oxide solution coated with the blend solution coated with the nano-cellulose and the silver nanowires are both controlled at 100 ℃, and the heat treatment time is controlled at 10.
Example 4
The application flexible composite transparent conductive film comprises a polyethylene terephthalate substrate layer, a blending layer of nano-cellulose and silver nanowires, and a graphene oxide layer, wherein the polyethylene terephthalate substrate layer is a PET substrate layer.
After the PET substrate layer is ultrasonically cleaned by acetone and isopropyl ketone and irradiated by ultraviolet-ozone, the following steps are sequentially carried out on the substrate: spin coating a blending solution, heat treating, spin coating a graphene oxide solution and heat treating, wherein the blending solution is a mixture of a silver nanowire solution and a nanocellulose solution, and the molar ratio of the silver nanowire to the nanocellulose is 1: 1, spin-coating the blended solution on the surface of the PET substrate layer, wherein the coating which is fixed on the surface of the PET substrate layer after the blended solution is subjected to heat treatment and drying is the blended layer of the nanocellulose and the silver nanowires;
spin-coating a graphene oxide solution on the blending layer of the nanocellulose and the silver nanowires, and obtaining the graphene oxide layer as a coating fixed on the surface of the blending layer of the nanocellulose and the silver nanowires after heat treatment and drying;
thus, a polyethylene terephthalate substrate layer, a blend layer of the nanocellulose and the silver nanowires, and a graphene oxide layer which are sequentially contacted are obtained.
Example 5
The application flexible composite transparent conductive film comprises a polyethylene terephthalate substrate layer, a blending layer of nano-cellulose and silver nanowires, and a graphene oxide layer, wherein the polyethylene terephthalate substrate layer is a PET substrate layer.
After the PET substrate layer is ultrasonically cleaned by acetone and isopropyl ketone and irradiated by ultraviolet-ozone, the following steps are sequentially carried out on the substrate: spin coating a blending solution, heat treating, spin coating a graphene oxide solution and heat treating, wherein the blending solution is a mixture of a silver nanowire solution and a nanocellulose solution, and the molar ratio of the silver nanowire to the nanocellulose is 1: 2, spin-coating the blended solution on the surface of the PET substrate layer, wherein the coating which is fixed on the surface of the PET substrate layer after the blended solution is subjected to heat treatment and drying is the blended layer of the nanocellulose and the silver nanowires;
spin-coating a graphene oxide solution on the blending layer of the nanocellulose and the silver nanowires, and obtaining the graphene oxide layer as a coating fixed on the surface of the blending layer of the nanocellulose and the silver nanowires after heat treatment and drying;
thus, a polyethylene terephthalate substrate layer, a blend layer of the nanocellulose and the silver nanowires, and a graphene oxide layer which are sequentially contacted are obtained.
Example 6
The application flexible composite transparent conductive film comprises a polyethylene terephthalate substrate layer, a blending layer of nano-cellulose and silver nanowires, and a graphene oxide layer, wherein the polyethylene terephthalate substrate layer is a PET substrate layer.
After the PET substrate layer is ultrasonically cleaned by acetone and isopropyl ketone and irradiated by ultraviolet-ozone, the following steps are sequentially carried out on the substrate: spin coating a blending solution, heat treating, spin coating a graphene oxide solution and heat treating, wherein the blending solution is a mixture of a silver nanowire solution and a nanocellulose solution, and the molar ratio of the silver nanowire to the nanocellulose is 1: 3, spin-coating the blended solution on the surface of the PET substrate layer, wherein the coating which is fixed on the surface of the PET substrate layer after the blended solution is subjected to heat treatment and drying is the blended layer of the nanocellulose and the silver nanowires;
spin-coating a graphene oxide solution on the blending layer of the nanocellulose and the silver nanowires, and obtaining the graphene oxide layer as a coating fixed on the surface of the blending layer of the nanocellulose and the silver nanowires after heat treatment and drying;
thus, a polyethylene terephthalate substrate layer, a blend layer of the nanocellulose and the silver nanowires, and a graphene oxide layer which are sequentially contacted are obtained.
Comparative example 1
The method comprises the following specific steps:
(1) and (3) taking 20 mg/ml silver nanowire raw solution, diluting to 5mg/ml, and placing in a reagent bottle.
(2) Preparing 5mg/ml graphene oxide solution, and carrying out ultrasonic treatment for 10 hours to ensure uniform dispersion.
(3) A square 1.5X 1.5 cm2 PET substrate was cut and marked.
(4) And (3) placing the PET substrate in the step (3) on dust-free cloth, cleaning the surface of the PET substrate with cleaning liquid, then placing the PET substrate in a beaker with a polytetrafluoroethylene cleaning rack, respectively pouring acetone and isopropanol, cleaning the PET substrate for 10 min under the ultrasonic condition, drying the PET substrate, and then placing the PET substrate in a UV-O3 irradiation machine for ultraviolet-ozone treatment for 10 min.
(5) And (3) heating the substrate to a specified temperature in advance by a heat treatment machine, taking the prepared solution in the step (1) and the solution in the step (2) and the treated substrate in the step (4), and carrying out spin coating to prepare the flexible transparent conductive film. Firstly, cleaning the surface of a substrate by using a spray gun (the surface of the substrate placed in a culture dish is contacted with the atmosphere when the substrate is taken out from an irradiation machine, and some dust is unavoidable, the substrate can be blown off by using the spray gun), then sequentially carrying out blended solution spin coating-heat treatment-graphene oxide solution spin coating-heat treatment on the substrate, wherein the spin coating speed is controlled to be 1000-4000rpm, the spin coating time is controlled to be 30-60s, the spin coating acceleration is 100-200 rpm/s, the heat treatment temperature is controlled to be 80-150 ℃, and the heat treatment time is controlled to be 5-20 min, thus obtaining the flexible composite transparent conductive film 1 for the comparative example.
Comparative example 2
The method comprises the following specific steps:
(1) and (3) taking 20 mg/ml silver nanowire raw solution, diluting to 5mg/ml, and placing in a reagent bottle.
(2) Taking 2.5 +/-0.5% of nano-cellulose solution, diluting to 2.5%, and placing in a reagent bottle.
(3) Uniformly mixing the appropriate amount of the solution in the step (1) and the solution in the step (2), wherein the mixing ratio is 1: and 3, placing the mixture in a reagent bottle for standby use.
(4) A square 1.5X 1.5 cm2 PET substrate was cut and marked.
(5) And (3) placing the PET substrate in the step (4) on dust-free cloth, cleaning the surface of the PET substrate with cleaning liquid, then placing the PET substrate into a beaker with a polytetrafluoroethylene cleaning rack, respectively pouring acetone and isopropanol, cleaning the PET substrate for 10 min under the ultrasonic condition, drying the PET substrate, and then placing the PET substrate into a UV-O3 irradiation machine for ultraviolet-ozone treatment for 10 min.
(6) And (4) preheating the heat treatment machine to a specified temperature, taking the prepared solution in the step (3) and the treated substrate in the step (5), and carrying out spin coating to prepare the flexible transparent conductive film. Firstly, cleaning the surface of a substrate by using a spray gun (the surface of the substrate is contacted with the atmosphere when the substrate is taken out of an irradiation machine and placed in a culture dish, and some dust is unavoidable, the substrate is blown off by using the spray gun), then sequentially carrying out blended solution spin coating-heat treatment-graphene oxide solution spin coating-heat treatment on the substrate, wherein the spin coating speed is controlled to be 1000-4000rpm, the spin coating time is controlled to be 30-60s, the spin coating acceleration is 100-200 rpm/s, the heat treatment temperature is controlled to be 80-150 ℃, and the heat treatment time is controlled to be 5-20 min, thus obtaining the flexible composite transparent conductive film 2 for the comparative example.
Comparative example 3
The method comprises the following specific steps:
(1) and (3) taking 20 mg/ml silver nanowire raw solution, diluting to 5mg/ml, and placing in a reagent bottle.
(2) A square 1.5X 1.5 cm2 PET substrate was cut and marked.
(3) And (3) placing the PET substrate in the step (2) on dust-free cloth, cleaning the surface of the PET substrate with cleaning liquid, then placing the PET substrate into a beaker with a polytetrafluoroethylene cleaning rack, respectively pouring acetone and isopropanol, cleaning the PET substrate for 10 min under the ultrasonic condition, drying the PET substrate, and then placing the PET substrate into a UV-O3 irradiation machine for ultraviolet-ozone treatment for 10 min.
(4) And (3) preheating the heat treatment machine to a specified temperature, taking the prepared solution in the step (1) and the treated substrate in the step (3), and carrying out spin coating to prepare the flexible transparent conductive film. Firstly, cleaning the surface of a substrate by using a spray gun (the surface of the substrate is contacted with the atmosphere when the substrate is taken out of an irradiation machine and placed in a culture dish, and some dust is unavoidable, the substrate is blown off by using the spray gun), then sequentially carrying out blended solution spin coating-heat treatment-graphene oxide solution spin coating-heat treatment on the substrate, wherein the spin coating speed is controlled to be 1000-4000rpm, the spin coating time is controlled to be 30-60s, the spin coating acceleration is 100-200 rpm/s, the heat treatment temperature is controlled to be 80-150 ℃, and the heat treatment time is controlled to be 5-20 min, thus obtaining the flexible composite transparent conductive film 3 for the comparative example.
Test method
The flexible composite transparent film prepared in example 1 was subjected to a mechanical stability test using a cyclic inside bending method with different radii, and a recovery resistance test after being subjected to stretching bending 200 times in different directions, and the results are shown in fig. 1. The flexible composite transparent film prepared by the scheme has high mechanical stability and strong flexibility; the flexible composite transparent film prepared in the embodiment 1 is prevented from being in the air, and the square resistance from the first to the fourth sides of the flexible composite transparent film is tested, and the result is shown in fig. 2, which shows that the flexible composite transparent film prepared in the scheme has relatively stable square resistance value and is not easy to be oxidized; the conductivity and the uniformity of the flexible composite transparent thin films prepared in example 1 and comparative examples 1 to 3 were tested by using a four-probe resistance tester, wherein the uniformity can be expressed by S = μ/M (μ is the maximum difference between the square resistance value and the average value of each point of the test), and the result is shown in fig. 3, which illustrates that the flexible composite transparent thin film prepared by the present scheme has good and uniform conductivity; when the flexible composite transparent thin films described in example 1 and comparative examples 1 to 3 were tested, the transmittance and the transmittance of visible light were important indicators for measuring the performance of the conductive thin film, and the transmittance at a light wave with a wavelength of 550nm was used as the test light to test the transmittance, the result is shown in fig. 4, which indicates that the flexible composite transparent conductive thin film prepared by the present method has a transmittance higher than 90% and a good transmittance.
Specific embodiments of the present invention have been described above in detail.
It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, any technical solutions that can be obtained by a person skilled in the art through logical analysis, reasoning or limited experiments in the prior art based on the inventive concept should be within the scope of protection defined by the claims.
Claims (10)
1. The flexible composite transparent conductive film is characterized by comprising a polyethylene terephthalate substrate layer, a blending layer of nano-cellulose and silver nanowires and a graphene oxide layer which are sequentially contacted.
2. The flexible composite transparent conductive film according to claim 1, wherein the molar ratio of the silver nanowires to the nanocellulose is 1: 1-3.
3. The preparation method of the flexible composite transparent conductive film according to claim 1, comprising the following steps:
K1. pretreating the surface of the substrate to obtain a pretreated substrate;
K2. coating a blending solution of silver nanowires and nanocellulose on the surface of the pretreated substrate, and then carrying out heat treatment to obtain a composite substrate;
K3. and coating uniformly dispersed graphene oxide solution on the surface of the composite substrate, and then carrying out heat treatment to obtain the flexible composite transparent conductive film.
4. The method for preparing a flexible composite transparent conductive film according to claim 3, wherein the pretreatment step in the K1 comprises ultrasonic cleaning with acetone or isopropyl alcohol and irradiating with ultraviolet-ozone.
5. The method for preparing a flexible composite transparent conductive film according to claim 3, wherein the concentration of the silver nanowire solution is 1-5 mg/ml.
6. The method for preparing a flexible composite transparent conductive film according to claim 3, wherein the concentration of the nanocellulose solution is 0.5-2.5%.
7. The method for preparing a flexible composite transparent conductive film according to claim 3, wherein the concentration of the graphene oxide solution is 1-5 mg/ml.
8. The method as claimed in claim 3, wherein the spin coating speed is 1000-4000rpm, the spin coating time is 30-60s, and the spin coating acceleration is 100-200 rpm/s.
9. The method for preparing the flexible composite transparent conductive film according to claim 3, wherein the heat treatment temperature in the K2 step is 80-150 ℃, and the heat treatment time is 5-20 min.
10. The method for preparing the flexible composite transparent conductive film according to claim 3, wherein the heat treatment temperature in the K3 step is 80-100 ℃, and the heat treatment time is 5-10 min.
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| CN104934108A (en) * | 2014-12-31 | 2015-09-23 | 重庆元石石墨烯技术开发有限责任公司 | Metallic nanowire-graphene bridge structural composite material and preparation method thereof |
| CN104882223A (en) * | 2015-04-27 | 2015-09-02 | 国家纳米科学中心 | Oxidized graphene/silver nanowire composite transparent conducting thin film and preparation method thereof |
| CN110223800A (en) * | 2019-06-25 | 2019-09-10 | 武汉工程大学 | A kind of preparation method of biodegradable flexible transparent conductive film |
| CN110797140A (en) * | 2019-11-13 | 2020-02-14 | 东南大学 | Silver nanowire and graphene composite flexible transparent conductive film and preparation method thereof |
| CN111029037A (en) * | 2019-11-21 | 2020-04-17 | 浙江大学 | Preparation method of high-stability silver nanowire/graphene oxide composite transparent conductive film |
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| CN112971725A (en) * | 2021-02-10 | 2021-06-18 | 武汉理工大学 | Preparation of electromagnetic radiation resistant nanocellulose/silver nanowire flexible sensor |
| CN112971725B (en) * | 2021-02-10 | 2023-12-26 | 武汉理工大学 | Preparation of electromagnetic radiation resistant nanocellulose/silver nanowire flexible sensor |
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