Preparation method of fishnet-shaped conductive electrode based on degradable substrate and electronic device

Abstract

The present application belongs to the technical field of fishing net-shaped conductive electrodes, and provides a fishing net-shaped conductive electrode preparation method based on a degradable substrate and electronic equipment. The fishing net-shaped conductive electrode preparation method based on the degradable substrate comprises the following steps: adding a hydrophobic modifier to a one-dimensional conductive material nanowire solution, so that the mass ratio of the hydrophobic modifier to the one-dimensional conductive material nanowire solution reaches 1:10; cleaning a flat degradable substrate; after the surface of the degradable substrate is dried, the one-dimensional conductive material nanowire solution to which the hydrophobic modifier is added is vertically applied to the surface of the degradable substrate; the degradable substrate is heated, so that the solvent on the surface of the degradable substrate is completely volatilized, and a fishing net-shaped conductive network is formed; a degradable polymer solution is coated on the surface of the degradable substrate with the fishing net-shaped conductive network, and then heating and solidification are performed, so that a flexible conductive film is formed; after the degradable substrate and the flexible conductive film are cooled, the two are separated, and a fishing net-shaped conductive electrode is obtained.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of fishing net-shaped conductive electrodes, and particularly relates to a fishing net-shaped conductive electrode preparation method based on a degradable substrate and an electronic device. BACKGROUND

[0002] The statements in this section merely provide background information related to the present application and do not necessarily constitute prior art.

[0003] One-dimensional conductive material nanowire-based (such as silver nanowire-based) transparent conductive electrodes have the advantages of strong bending stability, high transparency, low sheet resistance, and simple preparation process and low cost, and are the main materials for future transparent film production and manufacturing. The current manufacturing process of one-dimensional conductive material nanowire electrodes (such as silver nanowire electrodes) mainly includes drop coating, spin coating, template method, and Mayer rod coating, but in the above-mentioned manufacturing processes, the nanowires are still randomly arranged, and the cross-stacking state between the nanowires causes a large junction resistance. In addition, since the resistance at the connection of the one-dimensional conductive material nanowires is higher than that at other positions, when the current passes through the connection, the Joule heat generated will cause the temperature at the junction to be higher than that at other positions, forming a local "hot spot". After the current flows through the electrode for a period of time, the one-dimensional conductive material nanowires gradually decompose into discontinuous fragments. The "hot spot" effect has a great influence on the electro-thermal stability of the flexible electrode, and therefore a new structure is urgently needed to solve the "hot spot" problem of the conductive film. SUMMARY

[0004] In order to solve the technical problems in the background art, the present application provides a fishing net-shaped conductive electrode preparation method based on a degradable substrate and an electronic device, which solves the problem of large roughness of the degradable substrate, is conducive to the formation of a fishing net-shaped conductive electrode, has better sheet resistance uniformity, and at the same time, the arrangement mode of the nanowires formed during the deposition process is side-by-side arrangement, solving the "hot spot" problem caused by the random structure. The prepared flexible conductive film retains more voids to allow visible light to pass through, has higher transmittance, and at the same time, the conductive path of the fishing net-shaped electrode is more explicit, and the sheet resistance is lower and more uniform.

[0005] In order to achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0006] The first aspect of the present application provides a fishing net-shaped conductive electrode preparation method based on a degradable substrate.

[0007] In one or more embodiments, a fishing net-shaped conductive electrode preparation method based on a degradable substrate is provided, which comprises:

[0008] The hydrophobic modifier is added to the one-dimensional conductive material nanowire solution, so that the mass ratio of the hydrophobic modifier to the one-dimensional conductive material nanowire solution reaches 1:10;

[0009] cleaning the flat degradable substrate, and then applying a solution of one-dimensional conductive material nanowires to the surface of the degradable substrate vertically when the surface of the degradable substrate is dry;

[0010] heating the degradable substrate to make the solvent on the surface of the degradable substrate evaporate completely, forming a fishnet-like conductive network;

[0011] applying a solution of degradable polymer to the surface of the degradable substrate with the fishnet-like conductive network, and then heating and solidifying to form a flexible conductive film;

[0012] separating the degradable substrate and the flexible conductive film after cooling, to obtain a fishnet-like conductive electrode.

[0013] As an embodiment, the degradable substrate is a petal substrate or a leaf substrate.

[0014] As an embodiment, the one-dimensional conductive material nanowires are silver nanowires, copper nanowires, gold nanowires, or carbon nanotubes.

[0015] As an embodiment, when the one-dimensional conductive material nanowires are silver nanowires, the concentration ranges from 0.1 mg / ml to 10 mg / ml, the diameter ranges from 10 nm to 200 nm, and the length ranges from 1 um to 500 um.

[0016] As an embodiment, the way of applying the solution of one-dimensional conductive material nanowires to the surface of the degradable substrate vertically is spraying, dropping, or spin coating.

[0017] As an embodiment, the number of times of applying the solution of one-dimensional conductive material nanowires to the surface of the degradable substrate is at least once.

[0018] As an embodiment, when the number of times of applying the solution of one-dimensional conductive material nanowires to the surface of the degradable substrate is at least twice, the solution of one-dimensional conductive material nanowires is applied repeatedly after the previous solution of one-dimensional conductive material nanowires is dry.

[0019] As an embodiment, the temperature of heating the degradable substrate is 50℃, the heating time is 30 s, and the number of cycles of applying the solution of hydrophobic modifier is 3.

[0020] As an embodiment, the solution of degradable polymer is applied to the surface of the degradable substrate with the fishnet-like conductive network by spin coating.

[0021] A second aspect of the present application provides an electronic device.

[0022] An electronic device comprising a fishnet-like conductive electrode prepared by the method for preparing a fishnet-like conductive electrode based on a degradable substrate as described above.

[0023] Compared with the prior art, the present application has the following advantages:

[0024] (1) The present application changes the viscosity of the solution and the instantaneous contact angle when applied to the substrate by adding a hydrophobic modifier to the one-dimensional conductive material nanowire solution. The addition of the hydrophobic modifier to the solution makes the solution more viscous, reduces the flowability on the substrate, and is more easily pinned to the surface of the substrate. In addition, due to the addition of the hydrophobic modifier to the solution, the contact angle of the droplet on the substrate is larger when the solution is applied to the substrate, which is beneficial to pinning. In addition, the hydrophobic modifier also changes the volatility of the solution, which is better to some extent, so that the capillary force generated by the evaporation is larger, which is beneficial to the formation of the fishing net-like structure, which makes the sheet resistance uniformity of the fishing net-like structure better, and the arrangement of the nanowires formed during the deposition process is side-by-side, which solves the "hot spot" problem caused by random structure.

[0025] (2) The present application uses naturally occurring petals or leaves in nature as the substrate, the raw materials are simple and easy to obtain, the cost is low, and the biocompatibility is excellent. It can be naturally degraded in moist soil in nature, and can be completely decomposed in 96h under corrosion conditions.

[0026] (3) The present application adjusts the spraying process to make the nanowire arrangement present a fishing net-like structure, which reduces the number of cross arrangement of nanowires, reduces the junction resistance, reduces the number of "hot spots" in the film, enhances the electrothermal stability of the film, and retains more voids in the prepared conductive film to make the visible light transmission higher. At the same time, the fishing net-like electrode conductive path is more clear, and the sheet resistance is lower and more uniform.

[0027] The advantages of the additional aspects of the present application will be partially given in the following description, partially will become obvious from the following description, or will be understood by the practice of the present application. BRIEF DESCRIPTION OF DRAWINGS

[0028] The drawings accompanying the specification of the present application form a part thereof, serve to provide further understanding of the present application, and together with the description of the exemplary embodiments of the present application and their description serve to explain the present application, and do not constitute an improper limitation of the present application.

[0029] Figure 1 is a flow chart of the preparation method of the fishing net-like conductive electrode based on degradable substrate of the embodiment of the present application;

[0030] Figure 2 is an optical microscope pattern of the fishing net-like conductive electrode of the rose petal substrate of embodiment 1 of the present application;

[0031] Figure 3 is an optical microscope pattern of the fishing net-like conductive electrode of the peony petal substrate of embodiment 2 of the present application;

[0032] Figure 4 This is an optical microscope image of the net-shaped conductive electrode on the tulip petal substrate of Embodiment 3 of the present invention;

[0033] Figure 5 This is an optical microscope image of the net-like conductive electrode on the daffodil petal substrate of Embodiment 4 of the present invention;

[0034] Figure 6 This is an optical microscope image of the net-like conductive electrode on the rose petal substrate of Embodiment 5 of the present invention;

[0035] Figure 7 This is an optical microscope image of the fishing net-shaped conductive electrode based on the blade substrate in Embodiment 6 of the present invention;

[0036] Figure 8 This is the sheet resistance uniformity spectrum of the fishing net-shaped conductive electrode based on the blade substrate in Embodiment 7 of the present invention.

[0037] Figure 9 The chemical stability test results of the fishing net-shaped conductive electrode based on the blade substrate in Embodiment 8 of the present invention are shown.

[0038] Figure 10 This is a performance diagram of the electric heater based on the fishing net-shaped conductive electrode on the blade substrate in Embodiment 9 of the present invention;

[0039] Figure 11 This is a graph showing the morphological changes of the net-like conductive electrode based on the leaf substrate in Embodiment 9 of the present invention after being immersed in NaOH (pH=13.0) solution for different times.

[0040] Figure 12 This is an optical microscope image of the conductive network on the surface of a comparative glass substrate according to the present invention.

[0041] Figure 13 The contact angle of the droplet on the substrate surface when the hydrophobic modifier dosage is 1:1 (one-dimensional conductive material solution ratio).

[0042] Figure 14 This is an optical image of a conductive electrode formed when the ratio of hydrophobic modifier to one-dimensional conductive material solution is 1:1.

[0043] Figure 15 The contact angle of the droplet on the substrate surface when the hydrophobic modifier dosage is 1:50 (one-dimensional conductive material solution ratio).

[0044] Figure 16 This is an optical image of a conductive electrode formed when the ratio of hydrophobic modifier to one-dimensional conductive material solution is 1:50. Detailed Implementation

[0045] The application will be further described below with reference to the drawings and examples.

[0046] It should be noted that the following detailed description is exemplary in nature and is intended to provide further description of the application. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.

[0047] It is to be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments consistent with the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and / or "comprising," when used in this specification, specify the presence of stated features, steps, operations, elements, components, and / or groups thereof, but do not preclude the presence or addition of one or more other features, steps, operations, elements, components, and / or groups thereof.

[0048] Terminology:

[0049] Hot spots:

[0050] In material science, particularly in the application of transparent conductive films (TCF) involving nanowires such as AgNWs (silver nanowires), "hot spots" refer to localized high temperature regions generated at junctions when current flows through the thin film. These hot spots typically occur at the junctions formed by the intersection of silver nanowires, as these junctions have relatively high resistance. When current passes through these high-resistance junctions, Joule heating occurs, causing the temperature at the junctions to rise. If this high-temperature state persists, Joule heating will cause the silver nanowires to decompose at these hot spots, thereby affecting the electrical conductivity and mechanical stability of the entire network. Prolonged current flow can lead to the interruption of the conductive path, the rupture of the junctions, and over time, these hot spots can expand due to the continuous rise in temperature, ultimately leading to the performance degradation or failure of the silver nanowire-based transparent conductive film due to the accumulation of Joule heat. This phenomenon not only shortens the service life of the device, but also can cause deformation or damage to the device substrate due to continuous heat accumulation.

[0051] Fishing net-like structure:

[0052] When a solution of one-dimensional conductive material nanowires of a certain concentration is deposited on a substrate by spraying, dropping or blade coating, a "coffee ring" effect is produced. First, the surface tension of the substrate and the solution of one-dimensional conductive material nanowires should be matched, so that the droplet can be pinned on the substrate without rolling or shrinking; second, the solvent should have the characteristics of rapid evaporation, such as methanol, ethanol or isopropanol, etc. In this way, the evaporation rate at the edge of the rapidly evaporating droplet is faster than the evaporation rate in the middle, and there is a strong outward capillary flow, which can weaken the inward Marangoni backflow caused by the surface tension gradient, thereby driving the deposition of one-dimensional conductive material nanowires at the edge of the droplet, forming a uniform and ordered fishnet-like structure composed of large-size junctions and bundles.

[0053] Figure 1 is a flow chart of a preparation method of a fishnet-like conductive electrode based on a degradable substrate according to an embodiment of the present application. As shown in Figure 1 , the preparation method of a fishnet-like conductive electrode based on a degradable substrate according to an embodiment of the present application comprises the following steps:

[0054] Step 1: Add a hydrophobic modifier to the solution of one-dimensional conductive material nanowires, so that the mass ratio of the hydrophobic modifier to the solution of one-dimensional conductive material nanowires reaches 1:10.

[0055] The hydrophobic modifier includes but is not limited to the organic silicon hydrophobic modifier of Xingyao Chemical Industry, the glass nano self-cleaning liquid of Hongzhe Spider BOS-04 series, the easy-to-clean nano liquid of Nanmei Chi F-6000, and the waterproof agent of hahne / hanneng.

[0056] The hydrophobic modifier contains ester and lipid substances, which exhibit oiliness and hydrophobic properties. If the amount of the hydrophobic modifier added to the solution of one-dimensional conductive material nanowires is too much, the final solution of one-dimensional conductive material nanowires (containing the hydrophobic modifier) applied to the substrate exhibits a super-hydrophobic state, which is not conducive to the formation of the fishnet-like conductive electrode. If the amount of the hydrophobic modifier is too small, the modification cannot be achieved, and the droplet applied to the substrate is still hydrophilic, resulting in a random conductive network. Among them, the effect is best when the amount of the hydrophobic modifier: the solution of one-dimensional conductive material = 1:10.

[0057] When the amount of the hydrophobic modifier: the solution of one-dimensional conductive material = 1:1, the contact angle of the droplet on the surface of the substrate is as shown in Figure 13 According to the measurement, the contact angle is 167.996°. When the amount of the hydrophobic modifier: the solution of one-dimensional conductive material = 1:1, the optical image of the conductive electrode formed is as shown in Figure 14 .

[0058] When the amount of the hydrophobic modifier: the solution of one-dimensional conductive material = 1:50, the optical image of the conductive electrode formed is as shown in Figure 15 At this time, the contact angle of the droplet on the surface of the substrate is as shown inFigure 16 As shown, according to the measurement, the contact angle is 19.016°,

[0059] According to Figures 13-16 As can be seen from the data, when the hydrophobic modifier: one-dimensional metal nanomaterial solution is too small, a random conductive electrode is formed, and the performance is poor; when the hydrophobic modifier: one-dimensional metal nanomaterial solution is too large, separate points are formed on the surface of the substrate, and the substrate is not conductive.

[0060] Step 2: Clean the flat degradable substrate, and after the surface of the degradable substrate is dry, vertically apply the one-dimensional conductive material nanowire solution with the hydrophobic modifier to the surface of the degradable substrate.

[0061] In the embodiment of the present application, the degradable substrate is a petal substrate or a leaf substrate.

[0062] The petal includes but is not limited to rose petals, peony petals, tulip petals, narcissus petals, and Chinese rose petals, and the leaf includes but is not limited to Chinese scholar tree leaves, green ivy leaves, sycamore leaves, ginkgo leaves, maple leaves, elm leaves, poplar leaves, lilac leaves, and clover.

[0063] In one or more embodiments, during the preparation of the flat petal or leaf substrate, the petal or leaf is alternately cleaned with deionized water and anhydrous ethanol for a set period of time (such as 30s), and the surface is dried with nitrogen.

[0064] The size of the petal or leaf is 1cm 2 -10cm 2 The size of the petal and leaf can be specifically set according to actual conditions, which will not be described in detail here.

[0065] Since the substrate of the traditional silver nanowire-based conductive film is mostly polyethylene terephthalate (PET), polytetrafluoroethylene (PTFE), polyimide (PI), and polydimethylsiloxane (PDMS) and other organic high molecular polymers, such materials have greater ecological toxicity and are difficult to naturally degrade, which does not meet the needs of sustainable development of human society. In the present embodiment, the petal or leaf naturally existing in nature is used as the substrate, the raw materials are simple and easy to obtain, the cost is low, and the petal or leaf has excellent biocompatibility and can be naturally degraded in the moist soil in nature.

[0066] In the specific implementation process, the number of times of applying the one-dimensional conductive material nanowire solution to the surface of the degradable substrate is at least once (for example, 1-10 times).

[0067] When the number of times of applying the one-dimensional conductive material nanowire solution to the surface of the degradable substrate is at least twice, the one-dimensional conductive material nanowire solution is repeatedly applied after the previous one-dimensional conductive material nanowire solution is dry.

[0068] Preferably, the temperature of the degradable substrate is heated to 50°C, the heating time is 30s, and the number of cycles of the hydrophobic solution or the hydrophobically modified solution applied is 3.

[0069] In this embodiment, the hydrophobic modifier is added to the one-dimensional conductive material nanowire solution to make the dispersion more uniform. When the one-dimensional conductive material nanowire solution with the added hydrophobic modifier is applied to the substrate, the contact angle of the droplet with the surface of the degradable substrate increases. When the one-dimensional conductive material nanowire solution is drop-coated or sprayed onto the surface of the substrate, the increased contact angle ensures that the droplet does not spread, and the droplet can be pinned to the surface of the substrate. The solvent in the droplet will generate capillary force during the evaporation process, which will drive the one-dimensional conductive material nanowire to deposit at the edge of the droplet, which is conducive to the formation of a fishnet-shaped conductive electrode with better sheet resistance uniformity. At the same time, the deposition process forms a side-by-side arrangement of nanowires, which solves the "hot spot" problem caused by random structures.

[0070] In this embodiment, the one-dimensional conductive material nanowire includes but is not limited to silver nanowire, copper nanowire, gold nanowire, and carbon nanotube.

[0071] When the degradable substrate (petals and leaves) is used and the one-dimensional conductive material nanowire solution is selected as a silver nanowire solution, the silver nanowire in the one-dimensional conductive material nanowire solution has a diameter of 10-200 nm, and the length of the silver nanowire in the silver nanowire solution is 1-500 um. The concentration of the silver nanowire solution is 0.1 mg / ml-10 mg / ml.

[0072] Concentration range: 0.1 mg / ml-10 mg / ml. When the concentration is too large, it means that there are more silver nanowires in each droplet, and the capillary force required to drive the silver nanowires to form a fishnet-shaped conductive electrode is larger. When the concentration exceeds a certain range, the capillary force cannot drive the silver nanowires to form a fishnet-shaped conductive electrode. Through experiments, it is found that the maximum concentration is 10 mg / ml. When the concentration is too small, it has little effect on the formation of a fishnet-shaped conductive electrode structure. However, due to the small concentration, the amount of silver nanowires in the droplet is too small, and the number of applications required to form a fishnet-shaped conductive electrode is too large, which is inefficient. Therefore, the lower limit of the ideal concentration is 0.1 mg / ml.

[0073] The length and diameter of silver nanowires are larger, the weight of a single nanowire is heavier, and the ordered arrangement of silver nanowires is driven by capillary force generated by solvent evaporation. When the silver nanowires are thicker and longer, the driving force required is stronger, and if the driving force exceeds the limit that the solvent can provide, the fishnet-like structure cannot be formed. When the length and diameter of silver nanowires are smaller, the weight of a single nanowire is lighter, and the capillary force required is smaller, and the corresponding requirement for the volatility of the solvent is lower. However, too short nanowires will result in a larger number of nanowires required to complete a flexible electrode of the same size, which will increase the number of cross points per unit area, and the cross points are prone to cause high junction resistance and lead to electrical instability.

[0074] The dispersion solvent of the one-dimensional conductive material nanowire solution includes, but is not limited to, organic solvents such as methanol, ethanol, isopropanol, and water, and mixed solvents of several of the above solvents.

[0075] Preferably, the one-dimensional conductive material nanowire solution is applied to the surface of the degradable substrate by spraying. The liquid column of the one-dimensional conductive material nanowire solution sprayed is perpendicular to the surface of the degradable substrate.

[0076] The spraying method includes, but is not limited to, spraying the one-dimensional conductive material nanowire solution on the surface of the blade substrate by using a spray gun or an automatic spraying machine. The specific parameters of the spraying are as follows: the diameter of the nozzle of the spray gun is 0.1-12 mm, the distance from the nozzle to the degradable substrate is 1-80 cm, the carrier gas is an inert gas, the inert gas includes, but is not limited to, high-purity air, nitrogen, argon, etc., and the pressure of the carrier gas is 0.01-1 MPa.

[0077] The spraying parameters are also important factors affecting the surface morphology and performance of the one-dimensional conductive material nanowire fishnet-like conductive network, because they can affect the degree of atomization of the one-dimensional conductive material nanowire solution, i.e., the size of the droplets, and then affect the relationship between the evaporation rate of the droplets and capillary flow and Marangoni backflow, and finally affect the self-assembly behavior of the one-dimensional conductive material nanowires. As the pressure of the carrier gas decreases and the diameter of the spray gun nozzle increases, the grid of the fishnet-like structure formed also becomes larger. This shows that the microstructure, photoelectric performance of the electrode can be adjusted by a simple strategy, which shows the superiority of the method in simplicity and easy control.

[0078] The spraying application mode has high requirements on the surface contact angle of the substrate, and requires the surface contact angle of the substrate to be in the range of 55-160.6°. The contact angle of a conventional degradable substrate is in the range of 15-40°, and a liquid drop cannot be pinned, so it is difficult to form a fishing net-shaped conductive electrode. The fishing net-shaped conductive electrode can be realized by adding a hydrophobic modifier to a silver nanowire solution and adjusting the gas pressure and temperature during spraying. Specifically, a higher environmental temperature is conducive to the formation of a fishing net-shaped conductive electrode, and the temperature range for forming a fishing net-shaped conductive electrode is 15-50℃. The solvent ratio requires high volatility, but too high volatility can cause the silver nanowire to not be deposited to the edge of the liquid drop before the liquid drop is completely dried. Spraying is achieved by spraying gas to drive solvent evaporation and enhance capillary force, and the gas pressure range is 0.01 MPa-1 MPa.

[0079] Step 3: Heat the degradable substrate to completely volatilize the solvent on the surface of the substrate to form a fishing net-shaped conductive network.

[0080] For example, a constant temperature digital heating table is used to heat to ensure that the solvent on the surface of the flower petal substrate is completely volatilized, for example, the heating temperature is 30-70℃, and the drying time is 0.5-2h.

[0081] Step 4: Apply a degradable polymer solution to the surface of the degradable substrate with a fishing net-shaped conductive network, and then heat and solidify to form a flexible conductive film.

[0082] The degradable polymer solution includes, but is not limited to, a biodegradable solution such as polylactic acid (PLLA). The solid content in the liquid polylactic acid flexible substrate is 10-60%.

[0083] The degradable polymer solution is applied to the surface of the degradable substrate with a fishing net-shaped conductive network by a spin coating method, which can adjust the thickness of the flexible substrate and the flexible transparent electrode to adapt to the needs of different use scenarios. The rotation speed of the spin coater is 50-1500 rpm, and the spin coating time is 1-150 s.

[0084] The degradable polymer solution is solidified by heating, and the solidification heating temperature is 30-200℃, and the heating time is 10-200 min. The thickness of the flexible transparent electrode obtained by spin coating is 5-8000μm.

[0085] Step 5: After cooling, the degradable substrate and the flexible conductive film are separated to obtain a fishing net-shaped conductive electrode.

[0086] The fishing net-shaped conductive electrode prepared by the method of the embodiment of the present application has a simple preparation process and low production cost. The petals / leaves naturally occurring in nature are selected as the substrate, which has low ecological toxicity and can be naturally degraded. In addition, the fishing net-shaped conductive electrode has excellent photoelectric performance and electrothermal stability.

[0087] Example 1

[0088] (1) Silver nanowires with a diameter of 30 nm and a length of 20 um were selected and added to methanol to prepare a silver nanowire solution with a concentration of 0.4 mg / ml. The organic silicon hydrophobic modifier from Xingyao Chemical Co., Ltd. was added to the silver nanowire solution.

[0089] (2) A red rose petal with a size of about 2 cm x 2 cm was taken from nature, washed with deionized water and anhydrous ethanol alternately for 30 s, and the surface was dried with nitrogen.

[0090] (3) The red rose petal substrate obtained in step (2) was flatly attached to the surface of a 10 cm x 2.5 cm glass slide.

[0091] (4) 2 ml of the 0.4 mg / ml silver nanowire solution was measured by a pipette and added to a spray gun. The spray gun nozzle had a diameter of 0.3 mm, the shortest distance from the nozzle to the substrate was 5 cm, the spraying carrier gas was high-purity air, and the spraying pressure was 0.2 MPa.

[0092] (5) The moving speed of the spray gun was controlled at 10 cm / s, the spraying angle of the spray gun was adjusted so that the normal line of the silver nanowire liquid column was always perpendicular to the tangent of the surface of the red peony petal substrate at 90°, and a constant temperature digital heating table was used to set the temperature at 35°C. The heating time was 0.5 h, so that the solvent on the surface of the red rose petal substrate was completely volatilized, and a fishnet-shaped conductive electrode with uniform sheet resistance was formed on the surface of the red peony petal substrate. The optical microscope image of the fishnet-shaped conductive electrode of the rose petal substrate is shown in FIG. 1. The fishnet-shaped conductive electrode of the rose petal substrate has many remaining gaps, high visible light transmittance, clear conductive path of the fishnet-shaped electrode, low and uniform sheet resistance. Figure 2

[0093] (6) A 10% polylactic acid (PLLA) solution was coated on the surface of the rose petal substrate with a fishnet-shaped conductive network, a spin coater was set at a speed of 100 r / min for 50 s, and then placed in an oven for heating and curing at 60°C for 30 min to form a flexible conductive film. After the degradable substrate and the flexible conductive film were cooled, they were separated to obtain a fishnet-shaped conductive electrode.

[0094] Example 2

[0095] (1) Silver nanowires with a diameter of 30 nm and a length of 20 um were selected and added to ethanol to prepare a silver nanowire solution with a concentration of 0.5 mg / ml. The red spider BOS-04 series glass nanocleaning liquid was added to the silver nanowire solution.

[0096] ​(2) The red peony flower petals with a size of about 3 cm x 3 cm were taken from nature, washed with deionized water and anhydrous ethanol alternately for 30 s, and the surface was dried with nitrogen.

[0097] (3) The red peony flower petal substrate obtained in step (2) was flatly attached to the surface of a 6 cm x 6 cm glass slide.

[0098] (4) 2 ml of 0.5 mg / ml silver nanowire solution was taken by a pipette and added to a spray gun, the spray gun nozzle diameter was 0.3 mm, the shortest distance from the nozzle to the substrate was 6 cm, the spraying carrier gas was high-purity air, and the spraying pressure was 0.3 MPa.

[0099] (5) The moving speed of the spray gun was controlled at 10 cm / s, the spray angle of the spray gun was adjusted so that the normal line of the silver nanowire liquid column was always perpendicular to the tangent of the surface of the red peony flower petal substrate, and a constant temperature digital heating table was used to set the temperature to 35°C. The heating time was 0.5 h, so that the solvent on the surface of the red peony flower petal substrate was completely volatilized, and a square resistance uniform fishnet-shaped conductive electrode was formed on the surface of the red peony flower petal substrate. The optical microscope map of the fishnet-shaped conductive electrode of the peony flower petal substrate is shown in Figure 3 . The fishnet-shaped conductive electrode of the peony flower petal substrate has many remaining gaps, high visible light transmittance, clear conductive path of the fishnet-shaped electrode, low and uniform sheet resistance.

[0100] (6) A 20% polylactic acid (PLLA) solution was coated on the surface of the peony flower petal substrate with a fishnet-shaped conductive network, a spin coater was set at a speed of 200 r / min for 50 s, and then placed in an oven for heating and curing at 60°C for 30 min to form a flexible conductive film. After the degradable substrate and the flexible conductive film were cooled, they were separated, and a fishnet-shaped conductive electrode was obtained.

[0101] Example 3

[0102] (1) Silver nanowires with a diameter of 30 nm and a length of 20 um were selected and added to ethanol to prepare a silver nanowire solution with a concentration of 0.4 mg / ml; Nanmichi F-6000 easy-to-clean nano-hydrophobic modifier was added to the silver nanowire solution.

[0103] (2) White tulip petals with a size of about 2 cm x 2 cm were taken from nature, washed with deionized water and anhydrous ethanol alternately for 30 s, and the surface was dried with nitrogen.

[0104] (3) The red peony flower petal substrate obtained in step (2) was flatly attached to the surface of a 6 cm x 6 cm glass slide.

[0105] (4) 2 ml of 0.4 mg / ml silver nanowire solution was added into the spray gun by using a pipette, the nozzle diameter of the spray gun was 0.3 mm, the shortest distance between the nozzle and the substrate was 6 cm, the spraying carrier gas was high-purity air, and the spraying pressure was 0.3 MPa;

[0106] (5) The moving speed of the spray gun was controlled to be 10 cm / s, the spraying angle of the spray gun was adjusted so that the normal line of the silver nanowire liquid column was always perpendicular to the tangent of the white tulip petal substrate surface at 90°, and a constant temperature digital heating table was used to set the temperature to 35°C. The heating time was 0.5 h, so that the solvent on the surface of the white tulip petal substrate was completely volatilized, and it was ensured that a fishing net-shaped conductive electrode with uniform sheet resistance could be formed on the surface of the white tulip petal substrate. The optical microscope image of the fishing net-shaped conductive electrode of the tulip petal substrate is shown in FIG. 5. The fishing net-shaped conductive electrode of the tulip petal substrate has many remaining gaps, and the visible light transmittance is high. At the same time, the fishing net-shaped electrode has clear conductive path, low and uniform sheet resistance. Figure 4

[0107] (6) 30% polylactic acid (PLLA) solution was coated on the surface of the tulip petal substrate with the fishing net-shaped conductive network, the rotation speed of the spin coater was set to 300 r / min for 50 s, and then the tulip petal substrate was placed in an oven for heating and curing at 60°C for 30 min to form a flexible conductive film. After the degradable substrate and the flexible conductive film were cooled, they were separated, and the fishing net-shaped conductive electrode was obtained.

[0108] Example 4

[0109] (1) Silver nanowires with a diameter of 30 nm and a length of 20 um were selected and added to ethanol to prepare a silver nanowire solution with a concentration of 0.5 mg / ml, and a hahne / waterproof agent hydrophobic modifier was added to the silver nanowire solution.

[0110] (2) An appropriate size of about 2 cm x 2 cm white tulip petal was taken from nature, and was washed with deionized water and anhydrous ethanol alternately for 30 s, and the surface was dried with nitrogen.

[0111] (3) The red peony petal substrate obtained in step (2) was flatly attached to the surface of a 10 cm x 2.5 cm glass slide.

[0112] (4) 2 ml of 0.5 mg / ml silver nanowire solution was added into the spray gun by using a pipette, the nozzle diameter of the spray gun was 0.3 mm, the shortest distance between the nozzle and the substrate was 5 cm, the spraying carrier gas was high-purity air, and the spraying pressure was 0.2 MPa;

[0113] ​(5) Control the moving speed of the spray gun to be 10 cm / s, adjust the spraying angle of the spray gun so that the normal line of the silver nanowire liquid column is always perpendicular to the tangent of the surface of the white narcissus petal substrate at 90°, and use a constant temperature digital heating table to set the temperature to be 35°C. Heat for 0.5 h to make the solvent on the surface of the white narcissus petal substrate completely evaporate, and ensure that a fishing net-shaped conductive electrode with uniform sheet resistance can be formed on the surface of the white narcissus petal substrate. The optical microscope image of the fishing net-shaped conductive electrode of the narcissus petal substrate is shown in FIG. 5. Figure 5 The fishing net-shaped conductive electrode of the narcissus petal substrate has many remaining gaps, high visible light transmittance, clear conductive path of the fishing net-shaped electrode, low and uniform sheet resistance.

[0114] (6) 40% polylactic acid (PLLA) solution is coated on the surface of the narcissus petal substrate with the fishing net-shaped conductive network, the rotation speed of the spin coater is set to be 400 r / min for 50 s, and then the narcissus petal substrate is placed in an oven for heating and curing at 60°C for 30 min to form a flexible conductive film. After the degradable substrate and the flexible conductive film are cooled, the two are separated to obtain the fishing net-shaped conductive electrode.

[0115] Example 5

[0116] (1) Silver nanowires with a diameter of 30 nm and a length of 20 um are selected and added to ethanol to prepare a silver nanowire solution with a concentration of 0.4 mg / ml. Nanmochi F-6000 easy-to-clean nano-hydrophobic modifier is added to the silver nanowire solution.

[0117] (2) Appropriate pink rose petals with a size of about 4 cm x 4 cm are taken from nature, washed with deionized water and anhydrous ethanol alternately for 30 s, and the surface is dried with nitrogen.

[0118] (3) The pink rose petal substrate obtained in step (2) is flatly attached to the surface of an 8 cm x 8 cm glass slide.

[0119] (4) 2 ml of 0.4 mg / ml silver nanowire solution is taken by a pipette and added to a spray gun. The spray gun nozzle has a diameter of 0.3 mm, the shortest distance from the nozzle to the substrate is 5 cm, the spraying carrier gas is high-purity air, and the spraying pressure is 0.2 MPa.

[0120] (5) Control the moving speed of the spray gun to be 10 cm / s, adjust the spraying angle of the spray gun so that the normal line of the silver nanowire liquid column is always perpendicular to the tangent of the surface of the pink rose petal substrate at 90°, and use a constant temperature digital heating table to set the temperature to be 35°C. Heat for 0.5 h to make the solvent on the surface of the pink rose petal substrate completely evaporate, and ensure that a fishing net-shaped conductive electrode with uniform sheet resistance can be formed on the surface of the pink rose petal substrate. The optical microscope image of the fishing net-shaped conductive electrode of the narcissus petal substrate is shown in FIG. 5. Figure 6The fishnet-like conductive electrode of the rose petal substrate has high visible light transmittance, clear conductive path, low and uniform sheet resistance.

[0121] (6) 50% polylactic acid (PLLA) solution is coated on the surface of the rose petal substrate with the fishnet-like conductive network, a spin coater is set at a speed of 400 r / min for 50 s, and then placed in an oven for heating and curing at 60°C for 30 min to form a flexible conductive film. After the degradable substrate and the flexible conductive film are cooled, the two are separated to obtain the fishnet-like conductive electrode.

[0122] Example 6

[0123] In this embodiment, a fishnet-like conductive electrode based on a leaf substrate is provided, and the preparation method is as follows:

[0124] (1) Silver nanowires with a diameter of 30 nm and a length of 20 μm are added to methanol to prepare an Ag NWs solution with a concentration of 0.5 mg / ml, and a star-yao chemical organic silicon hydrophobic modifier is added to the Ag NWs solution.

[0125] (2) The Ag NWs solution with the star-yao chemical organic silicon hydrophobic modifier added is added to a spray gun, the nozzle diameter is 0.3 mm, the spraying distance is 10 cm, the Ag NWs solution is sprayed on a modified hackberry leaf substrate with a size of 2 cm x 2 cm, the sheet resistance is controlled to be about 50 Ω / sq, and the fishnet-like conductive network is formed after the solution volatilizes.

[0126] The optical microscope image of the fishnet-like conductive electrode based on the leaf substrate in Example 6 is shown in FIG. 6. Figure 7

[0127] Example 7

[0128] In this embodiment, a fishnet-like conductive electrode based on a leaf substrate is provided, and the preparation method is as follows:

[0129] (1) Silver nanowires with a diameter of 20 nm and a length of 30 μm are added to ethanol to prepare an Ag NWs solution with a concentration of 0.6 mg / ml, and a red spider BOS-04 series glass nano self-cleaning hydrophobic modifier is added to the Ag NWs solution.

[0130] (2) Then, the Ag NWs solution with the red spider BOS-04 series glass nano self-cleaning hydrophobic modifier added is added to a spray gun, the nozzle diameter is 0.5 mm, the spraying distance is 15 cm, the Ag NWs solution is sprayed on a green anthurium leaf substrate with a size of 6 cm x 6 cm, the sheet resistance is controlled to be about 10 Ω / sq, and the fishnet-like conductive network is formed after the solution volatilizes.

[0131] ​(3) Place the Epipremnum aureum leaf base forming a fishing net-like structure on a spin coater, and spin-coat a liquid polylactic acid solution onto the Epipremnum aureum leaf base coated with a fishing net-like structure of Ag NWs at a rotation speed of 900 rpm.

[0132] (4) Put the liquid polylactic acid and the Epipremnum aureum leaf base coated with a conductive network of a fishing net-like structure of Ag NWs into an oven and heat them at 60 °C for 40 min, and the above structure is cured into a film.

[0133] (5) After the Epipremnum aureum leaf base and the cured flexible conductive film are cooled, peel off the PLLA layer and the Ag NWs layer from the Epipremnum aureum leaf base to obtain a fishing net-like conductive electrode.

[0134] Figure 8 It is the map of the sheet resistance uniformity of the fishing net-like conductive electrode based on the leaf base in Example 7 of the present invention; the electrical performance of the sheet resistance uniformity of the fishing net-like conductive electrode in Example 7 is verified, and the sheet resistance uniformity is good, and the maximum change in sheet resistance is about 4%.

[0135] Example 8

[0136] [[ID=十六]]In this embodiment, a fishing net-like conductive electrode based on a tree leaf base is provided, and its preparation method is as follows:

[0137] (1) Select silver nanowires with diameters and lengths of 10 nm and 40 μm respectively, add them to ethanol to prepare an Ag NWs solution with a concentration of 0.4 mg / ml, and add a hahne / hanneng waterproof and hydrophobic modifier to the Ag NWs solution. [[ID=二十一]]

[0138] [[ID=二十二]](2) Then, add the above Ag NWs solution added with the hahne / hanneng waterproof and hydrophobic modifier to a spray gun with a nozzle diameter of 0.6 mm and a spraying distance of 18 cm, spray the Ag NWs solution on a 2 cm × 2 cm Firmiana simplex leaf base, control the sheet resistance to be about 20 Ω / sq, and wait for the solution to volatilize to form a fishing net-like conductive network.

[0139] (3) Place the Firmiana simplex leaf base forming a fishing net-like structure on a spin coater, and spin-coat a liquid polylactic acid solution onto the Firmiana simplex leaf base coated with a fishing net-like structure of Ag NWs at a rotation speed of 800 rpm.

[0140] (4) Put the liquid polylactic acid and the Firmiana simplex leaf base coated with a conductive network of a fishing net-like structure of Ag NWs into an oven and heat them at 50 °C for 60 min, and the above structure is cured into a film.

[0141] (5) After the cooling of the Ficus retusa leaf substrate and the cured flexible conductive film, the PLLA layer and the Ag NWs layer are peeled off from the Ficus retusa leaf substrate to obtain the fishnet-like conductive electrode.

[0142] The flexible conductive film in Example 8 is immersed in deionized water, ethanol, isopropanol, methanol and acetone for 2 hours, and the change of the sheet resistance is monitored to test the chemical stability as shown in FIG. 4. Figure 9

[0143] The flexible conductive film prepared in Example 8 is coated with conductive silver paste at both ends to increase the electrical contact, and after curing, a direct current voltage is provided on both sides of the electrode by a source table to test the electrical heater performance as shown in FIG. 5. Figure 10 Figure 11

[0144] Comparative Example

[0145] In this embodiment, a fishnet-like conductive electrode prepared on the surface of a glass substrate is provided. Glass is used as the substrate material, and other preparation methods are the same as those in Example 1, and the obtained conductive film is as shown in FIG. 6. Figure 12

[0146] In one or more embodiments, an electronic device is provided, which employs the fishnet-like conductive electrode prepared by the preparation method of the fishnet-like conductive electrode based on a degradable substrate as described above. The prepared flexible conductive film is widely used in flexible touch screens, flexible solar cells, electroluminescent devices, sensors, etc.

[0147] The fishnet-like conductive electrode of the embodiments of the present application is a degradable electrode, which can be applied in the fields of electrical heaters, electromagnetic interference shielding, sensors, smart windows and solar cells, etc.

[0148] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.​​​​

Claims

1. A method for fabricating a net-like conductive electrode based on a biodegradable substrate, characterized in that, include: A hydrophobic modifier is added to a one-dimensional conductive nanowire solution to achieve a mass ratio of 1:10 between the hydrophobic modifier and the one-dimensional conductive nanowire solution. The hydrophobic modifier includes Xingyao Chemical's organosilicon hydrophobic modifier, Red Spider BOS-04 series glass nano self-cleaning liquid, Namich F-6000 easy-clean nano liquid, and Hahne waterproofing agent. Clean and flatten the biodegradable substrate. After the surface of the biodegradable substrate is dry, apply a solution of one-dimensional conductive nanowire material with added hydrophobic modifier vertically to the surface of the biodegradable substrate. Heating the biodegradable substrate causes the solvent on its surface to evaporate completely, forming a net-like conductive network. A biodegradable polymer solution is coated onto the surface of a biodegradable substrate with a net-like conductive network, and then heated and cured to form a flexible conductive film. After cooling the biodegradable substrate and the flexible conductive film, the two are separated to obtain a net-like conductive electrode. The biodegradable substrate is a petal substrate or a leaf substrate.

2. The method for preparing a net-like conductive electrode based on a biodegradable substrate as described in claim 1, characterized in that, The one-dimensional conductive material nanowires are silver nanowires, copper nanowires, gold nanowires, or carbon nanotubes.

3. The method for preparing a net-like conductive electrode based on a biodegradable substrate as described in claim 1, characterized in that, When the one-dimensional conductive nanowire is silver nanowire, the concentration range is 0.1 mg / ml-10 mg / ml, the diameter range is 10-200 nm, and the length range is 1-500 μm.

4. The method for preparing a net-like conductive electrode based on a biodegradable substrate as described in claim 1, characterized in that, One-dimensional conductive nanowire solutions can be applied vertically to the surface of a biodegradable substrate by spraying, drop coating, or spin coating.

5. The method for preparing a net-like conductive electrode based on a biodegradable substrate as described in claim 1, characterized in that, The solution of one-dimensional conductive nanowires is applied to the surface of the biodegradable substrate at least once.

6. The method for preparing a net-like conductive electrode based on a biodegradable substrate as described in claim 5, characterized in that, When a one-dimensional conductive nanowire solution is applied to the surface of a biodegradable substrate at least twice, the one-dimensional conductive nanowire solution is applied again after the previous one-dimensional conductive nanowire solution has dried.

7. The method for preparing a net-like conductive electrode based on a biodegradable substrate as described in claim 1, characterized in that, The biodegradable substrate was heated to 50 °C for 30 seconds, and the hydrophobic modification solution was applied in 3 cycles.

8. The method for preparing a net-like conductive electrode based on a biodegradable substrate as described in claim 1, characterized in that, A biodegradable polymer solution was coated onto the surface of a biodegradable substrate with a net-like conductive network using a spin coating method.

9. An electronic device, characterized in that, It includes a net-shaped conductive electrode prepared by the method for preparing a net-shaped conductive electrode based on a biodegradable substrate as described in any one of claims 1-8.

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