CN113707368A - High-temperature-resistant transparent flexible conductive material and preparation method thereof - Google Patents
High-temperature-resistant transparent flexible conductive material and preparation method thereof Download PDFInfo
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- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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Abstract
The invention relates to a high-temperature-resistant transparent flexible conductive material, which comprises an inorganic high-temperature-resistant flexible transparent substrate, wherein a conductive layer is formed on the inorganic high-temperature-resistant flexible transparent substrate, and the conductive layer is composed of a material for forming a conductive network and an auxiliary conductive material for connecting the cross points of the conductive network. Compared with the prior art, the high-temperature-resistant transparent flexible conductive material prepared by the invention has the advantages of lower sheet resistance value, higher conductivity, better heat-resistant stability and better bending property, thereby effectively expanding the application range of the transparent flexible conductive material.
Description
Technical Field
The invention relates to the technical field of conductive film materials, in particular to a high-temperature-resistant transparent flexible conductive material and a preparation method thereof.
Background
The transparent conductive film is a film which can conduct electricity and has high transparency in a visible light range, is widely applied to new generation photoelectronic devices, can be used as an electrode of a perovskite solar cell, and can also be used as a substrate of devices such as a touch screen, wearable electronic equipment, a flat panel display, an organic light emitting diode, a sensor, an electronic shell and the like. Transparent conductive films based on rigid glass substrates are well established technologies, but their application fields are limited because they are not flexible. Therefore, the development of flexible transparent conductive films is receiving increasing attention. Most commonly, the conductive film is prepared by using a flexible material such as a polymer transparent resin as a substrate (for example, flexible acrylic, PET, PEN, etc.), and although the flexible conductive film has the advantages of flexibility, excellent light transmittance, wearability, etc., the use temperature range of the flexible conductive film is narrow (the film is deformed and damaged to be unusable at a temperature of more than 300 ℃), which greatly limits the application occasions of the flexible conductive film.
To this end, some researchers in the industry have proposed the preparation of flexible conductive films using inorganic transparent flexible materials as substrates, such as mica. Mica has the advantages of high temperature resistance, high transparency, good flexibility, heat conduction and radiation performance, high chemical stability and the like, and is really an excellent substrate material. However, mica itself has no conductivity, so that the flexible conductive film prepared by the prior art has lower conductivity and larger Sheet Resistance (Sheet Resistance), which leads to that the service performance of the flexible conductive film cannot be further improved, and the defects of the flexible conductive film are further amplified particularly when the flexible conductive film is used in some small wearable electronic devices or some precise instruments.
Disclosure of Invention
Technical problem to be solved
In view of the defects and shortcomings of the prior art, the invention provides the high-temperature-resistant transparent flexible conductive material and the preparation method thereof, and the inorganic high-temperature-resistant transparent flexible conductive film with lower sheet resistance value, higher conductivity, better heat-resistant stability and better bending property can be prepared, so that the application range of the inorganic high-temperature-resistant transparent flexible conductive film is expanded.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
in a first aspect, the present invention provides a high temperature resistant transparent flexible conductive material, which includes an inorganic high temperature resistant flexible transparent substrate, wherein a conductive layer is formed on the inorganic high temperature resistant flexible transparent substrate, and the conductive layer is composed of a material forming a conductive network and an auxiliary conductive material for connecting the cross points of the conductive network.
According to a preferred embodiment of the present invention, the inorganic high temperature-resistant flexible transparent substrate is a mica sheet. Preferably, the thickness is 0.1mm to 50cm
According to the preferred embodiment of the present invention, the material forming the conductive network is a conductive nanowire or a carbon nanotube; the auxiliary conductive material is fluorine-doped tin oxide FTO, indium tin oxide ITO, zinc oxide ZnO or aluminum-doped zinc oxide AZO.
In a second aspect, the present invention provides a method for preparing a high temperature resistant transparent flexible conductive material, comprising:
firstly, forming a conductive network on an inorganic high-temperature-resistant flexible transparent substrate by using a fiber or linear conductive material; and then connecting the cross points of the conductive network by using an auxiliary conductive material on the surface of the conductive network, thereby forming a conductive layer on the inorganic high-temperature-resistant flexible transparent substrate.
Preferably, the inorganic high-temperature-resistant flexible transparent substrate is a mica sheet, and the thickness of the mica sheet is 0.1 mm-50 cm.
According to a preferred embodiment of the invention, the method comprises:
s1, coating a material solution capable of forming a conductive network on the inorganic high-temperature-resistant flexible transparent substrate, and carrying out annealing treatment to form the conductive network on the inorganic high-temperature-resistant flexible transparent substrate;
and S2, coating a material solution capable of forming a conductive film on the surface of the conductive network, annealing, forming a conductive film outside the conductive network, and connecting the cross points of the conductive network together by the conductive film.
Preferably, the coating method is spin coating.
According to the preferred embodiment of the present invention, the material solution capable of forming the conductive network is a conductive nanowire solution, and the material solution capable of forming the conductive thin film is a fluorine-doped tin oxide FTO solution, an indium tin oxide ITO solution, a zinc oxide ZnO solution, or an aluminum-doped zinc oxide AZO solution.
According to a preferred embodiment of the present invention, in S1, the conductive nanowire solution is an ethanol solution of silver nanowires, and the concentration is 4-8 mg/ml; the annealing temperature is 50-300 ℃, and the annealing time is 5-30 min.
The ethanol solution of silver nanowires can be prepared by mixing commercially available silver nanowires and ethanol and then dispersing by ultrasonic, and the coating weight can be 40-250 μ l/cm2。
According to a preferred embodiment of the present invention, in S2, the material solution capable of forming the conductive thin film is an aluminum-doped zinc oxide AZO solution; the annealing temperature is 140-200 ℃. Wherein the concentration of the aluminum-doped zinc oxide AZO solution is 0.06 g/ml-0.08 g/ml, and the coating weight is 40 mul-250 mul/cm2. The doping amount of Al in the AZO is about 2 percent.
According to the preferred embodiment of the present invention, the annealing temperature in S2 is 200 ℃.
The preparation method of the aluminum-doped zinc oxide AZO solution comprises the following steps:
(1) dissolving zinc acetate dihydrate in ethanol, stirring vigorously, adding ethanolamine into the solution, and reacting at 40-55 deg.C under stirring;
(2) adding aluminum nitrate nonahydrate into the stirred solution, and stirring for reaction at 40-55 ℃;
(3) filtration through a 0.45 micron filter gave a clear AZO solution.
In a third aspect, the invention also relates to a high-temperature-resistant transparent flexible conductive material which is prepared by adopting the method in any one of the embodiments.
(III) advantageous effects
(1) When the high-temperature-resistant transparent flexible conductive material is prepared, the conductive network is formed on the substrate material, then the auxiliary conductive material capable of forming the conductive film is adopted to connect the cross points of the conductive network and fill the positions which cannot be covered by the conductive network to prepare the composite conductive layer, so that the prepared high-temperature-resistant transparent flexible conductive material has lower sheet resistance and higher conductivity, and the requirements of more application occasions are met. Meanwhile, the conductive network has a structure reinforcing effect on the conductive film formed by the auxiliary conductive material, and the problems of resistance increase of the conductive layer and the like caused by expansion, contraction, deformation, bending deformation and the like of the high-temperature resistant transparent flexible conductive material due to severe temperature change are solved.
(2) Compared with a flexible substrate such as PET (polyethylene terephthalate), the mica sheet is an inorganic material, has the advantages of high temperature resistance, high transparency, good flexibility (difficult fracture), excellent thermal conductivity (convenient heat dissipation), unique chemical stability such as acid and alkali resistance, light and heat aging resistance and the like, small thermal expansion coefficient (low deformation rate, and can be used for preparing high-precision optoelectronic instruments), small surface roughness, low cost and the like, and is an ideal flexible substrate material.
Drawings
Fig. 1 is a flow chart of the preparation of the high temperature resistant transparent flexible conductive material according to the preferred embodiment of the invention.
FIG. 2 shows the statistical results of the conductivity and sheet resistance of the high temperature resistant transparent flexible conductive material Mica-AgNW-AZO prepared in examples 1-6.
Fig. 3 is a SEM comparison graph of the high temperature resistant transparent flexible conductive material Mica-AgNW-AZO prepared in example 1 of the present invention and the high temperature resistant transparent flexible conductive material Mica-AgNW prepared in comparative example 1.
FIG. 4 is a plot of the sheet resistance of Mica-AgNW-AZO obtained at different annealing temperatures during the preparation of high temperature resistant transparent flexible conductive materials in examples 7-9.
FIG. 5 is a graph showing the square resistance test results at different positions of the high temperature resistant transparent flexible conductive materials prepared in examples 7-9.
FIG. 6 shows the surface change of the high temperature resistant transparent flexible conductive material Mica-AgNW-AZO of example 1 and the conventional PET-ITO after annealing at 500 ℃ under 200-.
FIG. 7 is a graph showing the square resistance of Mica-AgNW-AZO and the conventional PET-ITO of example 1 under heating at 200 ℃ as a function of time.
Fig. 8 shows the square resistance of the refractory transparent flexible conductive material Mica-AgNW-AZO of example 1 after being bent for 64 hours at different radii.
FIG. 9 is a curve of the sheet resistance of the high temperature resistant transparent flexible conductive material Mica-AgNW-AZO of example 1 as a function of the bending times.
Fig. 10 is a comparison of the high temperature resistant transparent flexible conductive material prepared in example 1 and the conventional PET-ITO sheet resistance as a function of the number of bending times (bending radius R ═ 4mm and 20 mm).
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
As shown in fig. 1, a flow chart of the preparation of the high temperature resistant transparent flexible conductive material according to the preferred embodiment of the present invention includes the following steps:
(1) and tearing off the protective films on two sides of the purchased mica sheet, and then sticking the mica sheet on a glass sheet stuck with double-sided adhesive to obtain glass-mica (mica is mica). In the experiment, the glass sheet and the mica sheet are both 1.5cm and 1.5cm, and the thickness of the mica sheet is 0.2 mm.
(2) Preparing an ethanol solution (preferably 4-10mg/ml) of silver nanowires (AgNW), shaking the solution uniformly, and setting the working parameters of a spin coater to be 2000r and 30 s. Placing the glass-mica on a spin coater for sucking, and vertically dripping 100 mu l of AgNW solution on the glass-mica; after spin coating, 100. mu.l of AgNW solution was dropped vertically onto the glass-mica, and spin coating was performed again at 2000r for 30 s. The total amount of spin coating of AgNW solution did not exceed 500 μ l.
(3) After the spin coating is finished, putting the glass-mica-AgNW on a heating panel, setting the temperature of the panel to be 50-300 ℃, heating for 5-30min, annealing and drying, and obtaining the conductive network of the silver nanowires on mica sheets (mica).
(4) Preparing a transparent AZO solution (the concentration is 0.060g/ml-0.080 g/ml). Putting the glass-mica-AgNW on a spin coater, and setting the working parameters of the spin coater as follows: 3000r, 30 s. And (3) taking 100 mu l of transparent AZO solution, vertically dropwise adding the solution on the glass-mica-AgNW, and carrying out spin coating. The dropwise addition of the AZO solution and the spin coating were repeated. The total amount of spin coating of the AZO solution does not exceed 500 μ l.
The preparation method of the AZO solution comprises the following steps: dissolving a certain amount of zinc acetate dihydrate in ethanol, stirring vigorously, adding a certain amount of ethanolamine into the solution, and reacting for 1h at 50 ℃ with stirring. To the stirred solution was added aluminum nitrate nonahydrate, and the reaction was stirred at 50 ℃ for 1 hour. Finally, filtration was carried out using a 0.45 μm filter to obtain a clear AZO solution.
(5) After the spin coating is finished, putting the glass-Mica-AgNW-AZO on the heating panel again, setting the temperature of the panel to be 140-.
According to the above process, the following examples of the high temperature resistant transparent flexible conductive material were prepared.
Examples 1 to 6
The high temperature resistant transparent flexible conductive material Mica-AgNW-AZO of examples 1-6 was prepared according to the following conditions.
| Parameter(s) | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| AgNW concentration | 5mg/ml | 4.5mg/ml | 4.5mg/ml | 6mg/ml | 5mg/ml | 4mg/ml |
| Amount of spin coating | 300μl | 300μl | 200μl | 300μl | 250μl | 200μl |
| |
140 |
140 |
140 |
140 |
140 |
140℃ |
| Annealing time | 15min | 15min | 15min | 15min | 15min | 15min |
| Concentration of AZO | 0.060g/ml | 0.066g/ml | 0.060g/ml | 0.066g/ml | 0.066g/ml | 0.060g/ml |
| Amount of spin coating | 300μl | 200μl | 300μl | 300μl | 300μl | 200μl |
| Annealing temperature | 180℃ | 180 |
200 |
200 |
200 |
200℃ |
| Annealing time | 10min | 10min | 5min | 10min | 10min | 10min |
As shown in FIG. 2, the sheet resistance and the conductivity of the 6 high temperature resistant transparent flexible conductive materials Mica-AgNW-AZO prepared in examples 1-6 were all 2-5 Ω/□, and the conductivity was 80-100S/m. The characteristics of small sheet resistance, large conductivity and good conductivity of the high-temperature-resistant transparent flexible conductive material Mica-AgNW-AZO prepared by the method are shown, and the requirements of practical application are met.
Comparative example 1
The preparation method and conditions of the embodiment 1 are used for preparing the high-temperature-resistant transparent flexible conductive material Mica-AgNW, and the specific method is as follows:
(1) and tearing off the protective films on two sides of the purchased mica sheet, and then sticking the mica sheet on a glass sheet stuck with double-sided adhesive to obtain glass-mica (mica is mica). The mica sheet specifications were the same as in example 1.
(2) Preparing an ethanol solution of 5mg/ml silver nanowires (AgNW), shaking the solution uniformly, and setting the working parameters of a spin coater as 2000r and 30 s. Placing the glass-mica on a spin coater for sucking, and vertically dripping 100 mu l of AgNW solution on the glass-mica; after spin coating, 100. mu.l of AgNW solution was dropped vertically onto the glass-mica, and spin coating was performed again at 2000r for 30 s. The total amount of spin coating of the AgNW solution was 300 μ l.
(3) After the spin coating is finished, the glass-Mica-AgNW is placed on a heating panel, the temperature of the panel is set to be 140 ℃, the panel is heated for 15min to be annealed and dried, the panel is taken out and placed in a culture dish until the temperature is reduced to room temperature, and the panel is peeled from the glass, so that the high-temperature-resistant transparent flexible conductive material Mica-AgNW is obtained.
The high temperature resistant transparent flexible conductive material Mica-AgNW-AZO of example 1 and the high temperature resistant transparent flexible conductive material Mica-AgNW of comparative example 1 were observed by an electron microscope, as shown in FIG. 3.
From the SEM image of fig. 3, it can be seen that: the conductive network formed by the silver nanowires in the Mica-AgNW is only formed by lapping the upper silver nanowires and the lower silver nanowires at the intersection without forming electric connection, so that the conductivity of the conductive layer in the high-temperature-resistant transparent flexible conductive material can be influenced. After the AZO solution is spin-coated on the conductive network and annealed, the AZO connects the intersection points of the silver nanowires together as can be seen from a high-power SEM image. The silver nanowires are completely connected with the silver nanowires in an embedded mode, contact points are increased, and the conductivity of the conducting layer is improved. The low-magnification SEM images show that the connections between the silver nanowires are very tight, so that the conductive layer of the Mica-AgNW-AZO is more conductive than the Mica-AgNW. And the actual conductivity test results confirm this expectation. The conductivity of the high temperature resistant transparent flexible conductive material prepared in example 1 is about 95S/m, while the conductivity of the Mica-AgNW prepared in comparative example 1 is only about 49S/m.
In summary, although Mica (Mica) has the characteristics of flexibility and high temperature resistance, it is not conductive, and when the Mica-AgNW flexible conductive material is prepared by spin-coating silver nanowires (AgNW), the conductivity of the flexible conductive material is affected due to the unconnected or insecure connection at the intersections of the silver nanowires and the silver nanowires. In the invention, the aluminum-doped zinc oxide (AZO) solution is spin-coated on the Mica-AgNW substrate, so that the intersection points of the silver nanowires and the silver nanowires can be fixed, the intersection points are tightly connected and form electric conduction, and the electric conductivity of the high-temperature-resistant transparent flexible conductive material Mica-AgNW-AZO is effectively improved.
Example 7
The preparation method and conditions of the embodiment 1 are used for preparing the high-temperature-resistant transparent flexible conductive material Mica-AgNW-AZO, and the specific method is as follows:
(1) and tearing off the protective films on two sides of the purchased mica sheet, and then sticking the mica sheet on a glass sheet stuck with double-sided adhesive to obtain glass-mica (mica is mica). The mica sheet specifications were the same as in example 1.
(2) Preparing an ethanol solution of 4mg/ml silver nanowires (AgNW), shaking the solution uniformly, and setting the working parameters of a spin coater as 2000r and 30 s. Placing the glass-mica on a spin coater for sucking, and vertically dripping 100 mu l of AgNW solution on the glass-mica; after spin coating, 100. mu.l of AgNW solution was dropped vertically onto the glass-mica, and spin coating was performed again at 2000r for 30 s. The total amount of spin coating of the AgNW solution was 200 μ l.
(3) After the spin coating is finished, the glass-mica-AgNW is placed on a heating panel, the temperature of the panel is set to be 140 ℃, the panel is heated for 15min, and annealing and drying are carried out, so that the conductive network of the silver nanowires is obtained on mica sheets (mica).
(4) A clear AZO solution of 0.060g/ml was prepared. Putting the glass-mica-AgNW on a spin coater, and setting the working parameters of the spin coater as follows: 3000r, 30 s. And (3) taking 100 mu l of transparent AZO solution, vertically dropwise adding the solution on the glass-mica-AgNW, and carrying out spin coating. The dropwise addition of the AZO solution and the spin coating were repeated. The total amount of spin coating of the AZO solution was 200. mu.l.
(5) After the spin coating is finished, putting the glass-Mica-AgNW-AZO on a heating panel again, setting the temperature of the panel to be 140 ℃, heating for 10min, taking out, putting the glass in a culture dish until the temperature is reduced to room temperature, and peeling the glass to obtain the high-temperature resistant transparent flexible conductive material Mica-AgNW-AZO.
Examples 8 to 9
Examples 8 and 9 were prepared by adjusting the annealing plate temperature after spin-coating the AZO solution in the step (5) to 200 ℃ and 300 ℃ respectively, based on example 7. Other steps and conditions were the same as in example 7.
The sheet resistivity and conductivity of examples 7-9 were tested and the results are shown in FIG. 4. It can be seen from the figure that the prepared Mica-AgNW-AZO has the smallest sheet resistance, the largest conductivity and the best conductivity when the annealing temperature is 200 ℃. Therefore, the performance of the prepared high-temperature-resistant transparent flexible conductive material Mica-AgNW-AZO is optimal when the annealing temperature is 200 ℃ after AZO is coated.
Referring to FIG. 5, it shows the sheet resistance of the Mica-AgNW-AZO conductive material prepared by AZO at different positions (schematic diagram in the figure) at annealing temperatures of 140 deg.C, 200 deg.C and 300 deg.C, respectively. The experimental result realizes that when the annealing temperature is 200 ℃, the sheet resistance of each position of the prepared conductive material is smaller than that of other positions, and the sheet resistances of five positions are very similar, and the uniformity of each part of the Mica-AgNW-AZO conductive material prepared at 200 ℃ is also very good.
Example 10
In order to further illustrate the superiority of the high-temperature-resistant transparent flexible conductive material Mica-AgNW-AZO compared with the conventional common flexible conductive material PET-ITO. The following is a comparison of the high temperature resistance of the two materials, respectively.
The comparison method comprises the following steps: the high temperature resistant transparent flexible conductive material Mica-AgNW-AZO prepared in example 1 and the back surface of the commercially available PET-ITO were respectively adhered with an adhesive tape, adhered to a glass sheet (1.5 cm. times.1.5 cm), and respectively placed on a heating panel at 200 ℃, 300 ℃, 400 ℃ and 500 ℃ for heating annealing.
As shown in fig. 6, the flexible conductive material PET-ITO exhibited a central bulge (central doming) when heated on a heating panel at 200 c. When the flexible conductive material PET-ITO is heated at 300 ℃ for 30 seconds and at 400 ℃ for 15 seconds, the phenomenon of bubbling and softening occurs, and the material is completely damaged and cannot be used. Correspondingly, the flexible conductive material Mica-AgNW-AZO prepared in the embodiment 1 of the invention is still intact even under the heating of 400 ℃, and the structure of the high-temperature resistant transparent flexible conductive material Mica-AgNW-AZO of the invention has high-temperature stability.
Example 11
In order to investigate the thermal stability of the conductivity of the high temperature resistant transparent flexible conductive material Mica-AgNW-AZO prepared by the present invention, in this example, the high temperature resistant transparent flexible conductive material Mica-AgNW-AZO prepared in example 1 was continuously heated on a heating panel at 200 ℃, and the change of the sheet resistance of the flexible conductive material with the increase of the heating time was tested. Meanwhile, PET-ITO (polyethylene terephthalate-indium tin oxide) which is a common flexible conductive material is used as a parallel control.
The results of the experiment are shown in FIG. 7. Wherein the right bar of the histogram represents PET-ITO and the left bar represents Mica-AgNW-AZO. From the figure results, the sheet resistance of the high-temperature-resistant transparent flexible conductive material Mica-AgNW-AZO prepared by the invention is increased very slowly along with the increase of the heating time, and the sheet resistance is only increased by about 1 time when the material is heated at 200 ℃ for 35 min. On the contrary, the sheet resistance of the flexible conductive material PET-ITO is increased by at least 40-50 times after being heated at 200 ℃ for 35 min.
Therefore, the conductivity of the high-temperature-resistant transparent flexible conductive material Mica-AgNW-AZO has high-temperature stability. This is mainly due to: first, the substrate material is a mica sheet with a very small coefficient of thermal expansion. Even under the condition of high-temperature heating, the mica sheet has no great expansion change. Secondly, the conductive layer on the surface of the high-temperature-resistant transparent flexible conductive material comprises a conductive network formed by silver nanowires, the cross points of the conductive network are connected and fixed by AZO conductive materials, so that the electric connectivity is improved, and the conductive film formed by AZO has strong high-temperature-resistant stability due to the reinforcing effect of the conductive network of the silver nanowires.
Example 12
Since the mechanical stability of the flexible conductive material is an important consideration for its application performance, in this example, a design experiment performed different radius bending on the refractory transparent flexible conductive material Mica-AgNW-AZO prepared in example 1. The change of the sheet resistance of the material with the extension of the bending time when bending is performed with different radii is measured simultaneously. The test results are shown in fig. 8.
As can be seen from the figure, after the high-temperature-resistant transparent flexible conductive material Mica-AgNW-AZO prepared by the invention is bent for 64 hours under different radiuses, the maximum sheet resistance is still below 25 omega/□, and the conductivity is still obviously higher than that of the common flexible conductive material PET-ITO. Therefore, the Mica-AgNW-AZO flexible conductive material prepared by the invention has very good mechanical stability.
Example 13
In this example, a design test was performed to bend the high temperature resistant transparent flexible conductive material Mica-AgNW-AZO prepared in example 1 at different radii, and the variation of sheet resistance of the material with increasing bending times when the material is bent at different radii was measured. The test results are shown in fig. 9.
As can be seen from the figure, after the high-temperature-resistant transparent flexible conductive material Mica-AgNW-AZO prepared by the invention is bent for 5000 times under different radiuses, the maximum sheet resistance is still below 25 omega/□, and the conductivity is still remarkably higher than that of the common flexible conductive material PET-ITO.
Therefore, the Mica-AgNW-AZO flexible conductive material prepared by the invention has very good mechanical stability.
Example 14
In this example, a design test was conducted on the high temperature resistant transparent flexible conductive material Mica-AgNW-AZO prepared in example 1, which was bent 5000 times with a bending radius R of 4mm and 20mm, and sheet resistances of the high temperature resistant transparent flexible conductive material Mica-AgNW-AZO at 1000 times, 2000 times, 3000 times, 4000 times, and 5000 times of bending were measured, respectively. Meanwhile, PET-ITO (polyethylene terephthalate-indium tin oxide) which is a common flexible conductive material is used as a parallel control.
The test results are shown in fig. 10. As can be seen from the figure, after the flexible conductive material with the bending radius of 20mm is bent 5000 times, the square resistance of the high temperature resistant transparent flexible conductive material Mica-AgNW-AZO is increased from 2.6 omega/□ to 13 omega/□, and meanwhile, the square resistance of the PET-ITO is increased from 9.6 omega/□ to 39.8 omega/□. After the flexible conductive material with the bending radius of 4mm is bent 5000 times, the square resistance of the high-temperature resistant transparent flexible conductive material Mica-AgNW-AZO is increased to 22.4 omega/□ from 4.4 omega/□, and meanwhile, the square resistance of the PET-ITO is increased to 47.2 omega/□ from 11 omega/□. The experiment shows that the conductivity and the mechanical stability of the high-temperature-resistant transparent flexible conductive material Mica-AgNW-AZO are obviously higher than those of PET-ITO.
The test results of examples 12-14 prove that the high temperature resistant transparent flexible conductive material prepared by the invention still maintains excellent electric conductivity after being bent with high strength and being bent for a plurality of times and for a long time. The high-temperature-resistant transparent flexible conductive material prepared by the invention has the advantages that the conductive layer on the surface of the high-temperature-resistant transparent flexible conductive material contains the conductive network formed by the silver nanowires, the cross points of the conductive network are connected and fixed by the AZO conductive material, so that the electric connectivity is improved, and the conductive film formed by the AZO has better structural stability due to the reinforcing effect of the conductive network of the silver nanowires.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The high-temperature-resistant transparent flexible conductive material is characterized by comprising an inorganic high-temperature-resistant flexible transparent substrate, wherein a conductive layer is formed on the inorganic high-temperature-resistant flexible transparent substrate, and the conductive layer is composed of a material for forming a conductive network and an auxiliary conductive material for connecting the cross points of the conductive network.
2. The high temperature resistant transparent flexible conductive material according to claim 1, wherein the inorganic high temperature resistant flexible transparent substrate is a mica sheet.
3. The high temperature resistant transparent flexible conductive material according to claim 1, wherein the material forming the conductive network is a conductive nanowire or a carbon nanotube; the auxiliary conductive material is fluorine-doped tin oxide FTO, indium tin oxide ITO, zinc oxide ZnO or aluminum-doped zinc oxide AZO.
4. A preparation method of a high-temperature-resistant transparent flexible conductive material is characterized by comprising the following steps: firstly, forming a conductive network on an inorganic high-temperature-resistant flexible transparent substrate by using a fiber or linear conductive material; and then connecting the cross points of the conductive network by using an auxiliary conductive material on the surface of the conductive network, thereby forming a conductive layer on the inorganic high-temperature-resistant flexible transparent substrate.
5. The method for preparing the inorganic high-temperature-resistant flexible transparent substrate according to claim 4, wherein the inorganic high-temperature-resistant flexible transparent substrate is a mica sheet.
6. The method of manufacturing according to claim 5, comprising:
s1, coating a material solution capable of forming a conductive network on the inorganic high-temperature-resistant flexible transparent substrate, and carrying out annealing treatment to form the conductive network on the inorganic high-temperature-resistant flexible transparent substrate;
and S2, coating a material solution capable of forming a conductive film on the surface of the conductive network, annealing, forming a conductive film outside the conductive network, and connecting the cross points of the conductive network together by the conductive film.
7. The preparation method according to claim 6, wherein the material solution capable of forming the conductive network is a conductive nanowire solution, and the material solution capable of forming the conductive thin film is a fluorine-doped tin oxide (FTO) solution, an Indium Tin Oxide (ITO) solution, a zinc oxide (ZnO) solution or an aluminum-doped zinc oxide (AZO) solution.
8. The preparation method according to claim 6, wherein in S1, the conductive nanowire solution is an ethanol solution of silver nanowires, and the concentration is 4-8 mg/ml; the annealing temperature is 90-300 ℃, and the annealing time is 5-30 min.
9. The method according to claim 6, wherein in S2, the material solution capable of forming the conductive film is an aluminum-doped zinc oxide AZO solution; the annealing temperature is 140-200 ℃.
10. The method according to claim 9, wherein the annealing temperature in S2 is 200 ℃.
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