Preparation method of fishing net-shaped conductive electrode based on degradable substrate and electronic equipment

Abstract

The invention belongs to the technical field of fishing net-shaped conductive electrodes, and provides a preparation method of a fishing net-shaped conductive electrode based on a degradable substrate and electronic equipment. The preparation method of the fishing net-shaped conductive electrode based on the degradable substrate comprises the following steps: adding a hydrophobic modifier into 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 and flattening the degradable substrate, and after the surface of the degradable substrate is dried, vertically applying the one-dimensional conductive material nanowire solution added with the hydrophobic modifier to the surface of the degradable substrate; heating the degradable substrate to completely volatilize the solvent on the surface of the degradable substrate to form a fishing net-shaped conductive network; coating the degradable polymer solution on the surface of the degradable substrate with the fishing net-shaped conductive network, and then heating and curing to form a flexible conductive film; after the degradable substrate and the flexible conductive film are cooled, the degradable substrate and the flexible conductive film are separated, and the fishing net-shaped conductive electrode is obtained.

Description

Technical Field

[0001] The invention belongs to the technical field of fishnet-shaped conductive electrodes, and in particular relates to a method for preparing a fishnet-shaped conductive electrode based on a degradable substrate and an electronic device. Background Art

[0002] The statements in this section merely provide background information related to the present invention 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 extremely strong bending stability, high transparency, low square resistance, simple preparation process and low cost, and are the main materials for the production and manufacturing of transparent films in the future. The current manufacturing processes of one-dimensional conductive material nanowire electrodes (such as silver nanowire electrodes) mainly include drop coating, spin coating, template method, Mayer rod coating method, etc., but in the above-mentioned manufacturing processes, the nanowires are still randomly arranged, and the cross-stacked state between nanowires causes a large junction resistance. In addition, since the resistance of the one-dimensional conductive material nanowire connection is higher than that of other positions, when the current passes through the connection, the Joule heat generated will cause the temperature at the node to be higher than that of other areas, forming a local "hot spot". After the current flows through the electrode for a period of time, the one-dimensional conductive material nanowire gradually decomposes into discontinuous fragments. The "hot spot" effect has a great influence on the electrothermal stability of flexible electrodes, so a new structure is urgently needed to solve the "hot spot" problem of conductive films. Summary of the invention

[0004] In order to solve the technical problems existing in the above-mentioned background technology, the present invention provides a method for preparing a fishnet-shaped conductive electrode 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 fishnet-shaped conductive electrode, and has better uniformity of square resistance. At the same time, the nanowires formed in the deposition process are arranged side by side, which solves the "hot spot" problem caused by the random structure. The prepared flexible conductive film retains more gaps to allow visible light to pass through, and the transmittance is higher. At the same time, the conductive path of the fishnet-shaped electrode is clearer, and the sheet resistance is lower and more uniform.

[0005] In order to achieve the above object, the present invention adopts the following technical solution:

[0006] The first aspect of the present invention provides a method for preparing a fishnet-shaped conductive electrode based on a degradable substrate.

[0007] In one or more embodiments, a method for preparing a fishnet-shaped conductive electrode based on a degradable substrate is provided, comprising:

[0008] Adding a hydrophobic modifier 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] The degradable substrate is cleaned and leveled, and after the surface of the degradable substrate is dried, a one-dimensional conductive material nanowire solution with a hydrophobic modifier added thereto is vertically applied to the surface of the degradable substrate;

[0010] The degradable substrate is heated to completely volatilize the solvent on its surface, thereby forming a fishnet-like conductive network;

[0011] The degradable polymer solution is coated on the surface of the degradable substrate having a fishnet-shaped conductive network, and then heated and cured to form a flexible conductive film;

[0012] After the degradable substrate and the flexible conductive film are cooled, the two are separated to obtain a fishnet-shaped 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 nanowire is silver nanowire, copper nanowire, gold nanowire or carbon nanotube.

[0015] As an embodiment, when the one-dimensional conductive material 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 um.

[0016] As an embodiment, the one-dimensional conductive material nanowire solution is vertically applied on the surface of the degradable substrate by spraying, dripping or spin coating.

[0017] As an embodiment, the one-dimensional conductive material nanowire solution is applied on the surface of the degradable substrate at least once.

[0018] As an embodiment, when the one-dimensional conductive material nanowire solution is applied on the surface of the degradable substrate at least twice, the one-dimensional conductive material nanowire solution is applied again after the previous one-dimensional conductive material nanowire solution is dried.

[0019] As an embodiment, the temperature at which the degradable substrate is heated is 50° C., the heating time is 30 seconds, and the number of cycles of applying the hydrophobic modification solution is 3 times.

[0020] As an implementation mode, the degradable polymer solution is coated on the surface of the degradable substrate having a fishnet-shaped conductive network by spin coating.

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

[0022] An electronic device comprises a fishnet-shaped conductive electrode prepared by the above-mentioned method for preparing a fishnet-shaped conductive electrode based on a degradable substrate.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] (1) The present invention 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. When the hydrophobic modifier is added to the solution, the solution becomes more viscous, the fluidity on the substrate is weakened, and it is easier to pin on the surface of the substrate. At the same time, since the hydrophobic modifier is added to the solution, when the solution is applied to the substrate, the contact angle of the droplet on the substrate becomes larger, which is conducive to pinning. In addition, the hydrophobic modifier also changes the volatility of the solution. To a certain extent, its volatility becomes better, so that the capillary force generated by volatilization becomes larger, which is conducive to the formation of a fishnet structure. This makes the square resistance uniformity of the fishnet structure better. At the same time, the nanowires formed in the deposition process are arranged side by side, which solves the "hot spot" problem caused by the random structure.

[0025] (2) The present invention uses petals or leaves naturally existing in nature as substrates. The raw materials are easy to obtain and low in cost. They have excellent biocompatibility and can be naturally degraded in moist soil in nature. They can be completely decomposed within 96 hours under corrosive conditions.

[0026] (3) The present invention arranges the nanowires in a fishnet-like structure by adjusting the spraying process. This structure reduces the number of cross-arrangements of the nanowires, lowers the junction resistance, and at the same time reduces the number of "hot spots" in the film, thereby enhancing the electrothermal stability of the film. In addition, the prepared conductive film retains more gaps to allow visible light to pass through, resulting in a higher transmittance. At the same time, the conductive path of the fishnet-like electrode is clearer, and the sheet resistance is lower and more uniform.

[0027] Advantages of additional aspects of the present invention will be given in part in the following description, and in part will become obvious from the following description, or will be learned through practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The accompanying drawings in the specification, which constitute a part of the present invention, are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute improper limitations on the present invention.

[0029] Figure 1 is a flow chart of a method for preparing a fishnet-shaped conductive electrode based on a degradable substrate according to an embodiment of the present invention;

[0030] Figure 2 is an optical microscope image of a fishnet-shaped conductive electrode on a rose petal substrate in Example 1 of the present invention;

[0031] Figure 3 is an optical microscope image of a fishnet-shaped conductive electrode on a peony petal substrate in Example 2 of the present invention;

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

[0033] Figure 5 is an optical microscope image of a fishnet-shaped conductive electrode on a narcissus petal substrate in Example 4 of the present invention;

[0034] Figure 6 This is an optical microscope image of a fishnet-shaped conductive electrode on a rose petal substrate in Example 5 of the present invention;

[0035] Figure 7 is an optical microscope image of a fishnet-shaped conductive electrode based on a blade substrate in Example 6 of the present invention;

[0036] Figure 8 is a graph of the uniformity of square resistance of a fishnet-shaped conductive electrode based on a blade substrate in Example 7 of the present invention;

[0037] Fig. 9 The chemical stability test result of the fishnet-shaped conductive electrode based on the blade substrate in Example 8 of the present invention;

[0038] Fig.10 is a performance diagram of an electric heater based on a fishnet-shaped conductive electrode on a blade substrate in Example 9 of the present invention;

[0039] Fig.11 This is a graph showing the morphological changes of the fishnet-shaped conductive electrode based on the blade substrate of Example 9 of the present invention after being immersed in a NaOH (pH=13.0) solution for different periods of time;

[0040] Fig.12 It is an optical microscope spectrum of the conductive network on the surface of the glass substrate of the comparative example of the present invention;

[0041] Fig.13 is the contact angle of the droplet on the substrate surface when the ratio of hydrophobic modifier dosage to one-dimensional conductive material solution is 1:1;

[0042] Fig.14 is an optical image of a conductive electrode formed when the amount of hydrophobic modifier: one-dimensional conductive material solution = 1:1;

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

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

[0045] The present invention will be further described below in conjunction with the accompanying drawings and embodiments.

[0046] It should be noted that the following detailed descriptions are all illustrative and intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used herein have the same meanings as those commonly understood by those skilled in the art to which the present invention belongs.

[0047] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit exemplary embodiments according to the present invention. As used herein, unless the context clearly indicates otherwise, the singular form is also intended to include the plural form. In addition, it should be understood that when the terms "comprising" and / or "including" are used in this specification, it indicates the presence of features, steps, operations, devices, components and / or combinations thereof.

[0048] Terminology explanation:

[0049] Hotspot:

[0050] In materials science, especially in applications involving transparent conductive films (TCFs) of nanowires such as AgNWs, “hot spots” are localized high-temperature regions generated at junctions when current flows through the film. These hot spots usually occur at junctions formed by the intersection of silver nanowires because the resistance of these junctions is relatively high. When current passes through these high-resistance junctions, Joule heat is generated, causing the temperature at the junctions to rise. If this high-temperature state persists, Joule heat will cause the silver nanowires to decompose at these hot spots, which in turn affects the conductivity and mechanical stability of the entire network. Long-term current flow may cause interruptions in the conductive path and rupture of the nodes, and over time, these hot spots may expand due to the continued increase in temperature, ultimately causing the silver nanowire-based transparent conductive film to degrade or fail due to the accumulation of Joule heat. This phenomenon not only shortens the service life of the device, but may also cause deformation or damage to the device substrate due to continuous heat accumulation.

[0051] Fishnet structure:

[0052] When a certain concentration of one-dimensional conductive material nanowire solution is deposited on a substrate by spraying, dripping or scraping, a "coffee ring" effect will occur. First, the surface tension of the substrate and the one-dimensional conductive material nanowire solution droplet must match, so that the droplet can be pinned on the substrate without rolling or shrinking; second, the solvent must have the characteristics of rapid evaporation, such as methanol, ethanol or isopropanol, so that the evaporation rate at the edge of the rapidly evaporating droplet is faster than the evaporation rate in the middle, and there will be a strong outward capillary flow, which can weaken the inward Marangoni reflux caused by the surface tension gradient, thereby driving the one-dimensional conductive material nanowire to deposit at the edge of the droplet, forming a uniform and orderly fishing net structure composed of large-sized knots and bundles.

[0053] Figure 1 FIG. 1 is a flow chart of a method for preparing a fishnet-shaped conductive electrode based on a degradable substrate according to an embodiment of the present invention. Figure 1 As shown, an embodiment of the present invention provides a method for preparing a fishnet-shaped conductive electrode based on a degradable substrate, comprising:

[0054] Step 1: Add a hydrophobic modifier 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.

[0055] The hydrophobic modifier includes but is not limited to Xingyao Chemical's organosilicon hydrophobic modifier, Red Spider BOS-04 series glass nano self-cleaning liquid, Namechi F-6000 easy-to-clean nano liquid, and hahne / Hanneng waterproofing agent.

[0056] The hydrophobic modifier contains esters and lipids, which show oily and hydrophobic properties. If too much hydrophobic modifier is added to the one-dimensional conductive material nano solution, the resulting one-dimensional conductive material nano solution (containing hydrophobic modifier) ​​will be super-hydrophobic when applied to the substrate, which is not conducive to the formation of a fishnet-shaped conductive electrode. If the amount of hydrophobic modifier is too little, it will not play a modifying role. When the droplets are applied to the substrate, they are still in a hydrophilic state, and the conductive network formed is a random state. Among them, the best effect is when the amount of hydrophobic modifier: one-dimensional conductive material solution = 1:10.

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

[0058] When the amount of hydrophobic modifier: one-dimensional conductive material solution = 1:50, the optical image of the conductive electrode formed is as follows Fig.15 As shown in Figure 2, at this time, the contact angle of the droplet on the substrate surface is as follows: Fig.16 As shown, according to the measurement, the contact angle is 19.016°.

[0059] according to Figure 13-Figure 16 From the data, we can see that when the hydrophobic modifier: one-dimensional metal nanomaterial solution is too small, random conductive electrodes are formed and the performance deteriorates; when the hydrophobic modifier: one-dimensional metal nanomaterial solution is too large, separated points are formed on the substrate surface and it is not conductive.

[0060] Step 2: Clean and level the degradable substrate, and after the surface of the degradable substrate is dried, vertically apply a one-dimensional conductive material nanowire solution to which a hydrophobic modifier is added to the surface of the degradable substrate.

[0061] The degradable substrate in the embodiment of the present invention is a petal substrate or a leaf substrate.

[0062] Among them, petals include but are not limited to rose petals, peony petals, tulip petals, daffodil petals, and rose petals; leaves include but are not limited to elm leaves, green radish leaves, sycamore leaves, ginkgo leaves, maple leaves, elm leaves, poplar leaves, lilac leaves, and clover leaves.

[0063] In one or more embodiments, in the process of preparing a flat petal or leaf substrate, the petals or leaves are alternately cleaned with deionized water and anhydrous ethanol for a set period of time (for example, 30 seconds), and the surface is blown dry with nitrogen.

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

[0065] Since the substrates of traditional silver nanowire-based conductive films are mostly organic polymers such as polyethylene terephthalate (PET), polytetrafluoroethylene (PTFE), polyimide (PI) and polydimethylsiloxane (PDMS), these materials have high ecotoxicity and are difficult to degrade naturally, which does not meet the needs of sustainable development of human society. In this embodiment, petals or leaves naturally existing in nature are used as substrates. The raw materials are easy to obtain and low in cost, and have excellent biocompatibility, and can be naturally degraded in moist soil in nature.

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

[0067] Wherein, when the number of times of applying the one-dimensional conductive material nanowire solution on 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 dried.

[0068] Preferably, the temperature at which the degradable substrate is heated is 50° C., the heating time is 30 seconds, and the number of cycles of applying the hydrophobic solution or the hydrophobic modified solution is 3 times.

[0069] This embodiment adopts a method of adding a hydrophobic modifier to a one-dimensional conductive material nanowire solution, wherein the hydrophobic modifier is added to the one-dimensional conductive material nanowire solution to make it more evenly dispersed, and when the one-dimensional conductive material nanowire solution with the hydrophobic modifier added is applied to the substrate, the contact angle between the droplet and the surface of the degradable substrate increases. When the one-dimensional conductive material nanowire solution is dripped or sprayed onto the substrate surface, the contact angle increases to ensure that the droplet does not spread, and the droplet can be pinned on the substrate surface. The solvent in the droplet will generate capillary force during the volatilization process, and the capillary force drives the one-dimensional conductive material nanowire to be deposited on the edge of the droplet, which is conducive to forming a fishnet-shaped conductive electrode with better uniformity of square resistance. At the same time, the nanowires formed during the deposition process are arranged side by side, which solves the "hot spot" problem caused by the random structure.

[0070] In this embodiment, the one-dimensional conductive material nanowires include but are not limited to silver nanowires, copper nanowires, gold nanowires and carbon nanotubes.

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

[0072] Concentration range: 0.1mg / ml–10mg / ml. When the concentration is too high, it is equivalent to more silver nanowires in each droplet. The capillary force required to drive the silver nanowires to form a fishnet-like conductive electrode is greater. Beyond a certain range, the capillary force cannot drive the silver nanowires to form a fishnet-like conductive electrode. Through experiments, it is found that the maximum concentration is 10mg / ml. When the concentration is too low, it will affect the formation of the fishnet-like conductive electrode structure, but because the concentration is too low, the amount of silver nanowires contained in the droplet is too small, so the number of applications required to form the fishnet-like conductive electrode is too many, and the efficiency is low. The ideal lower limit of concentration is 0.1mg / ml.

[0073] When the length and diameter of the silver nanowires are larger, the weight of a single nanowire is heavier. The orderly arrangement of the silver nanowires is driven by the capillary force generated by the evaporation of the solvent. When the silver nanowires are thicker and longer, the driving force required is stronger. If the driving force exceeds the limit that the solvent can provide, then the fishing net structure cannot be formed. When the length and diameter of the silver nanowires are smaller, the weight of a single nanowire is lighter, the capillary force required is smaller, and the corresponding requirement for the volatility of the solvent is lower. However, if the nanowires are too short, more nanowires are required to complete the same size of flexible electrodes, which will increase the number of nanowire intersections per unit area, and the intersections are prone to cause high junction resistance and lead to electrothermal 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, water, and a mixed solvent of the above-mentioned solvents.

[0075] Preferably, the one-dimensional conductive material nanowire solution is applied to the surface of the degradable substrate by spraying, wherein the sprayed one-dimensional conductive material nanowire solution column 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 using a spray gun or an automatic sprayer. 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, and 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] Spraying parameters are also important factors affecting the surface morphology and performance of the fishnet-like conductive network based on one-dimensional conductive material nanowires, because they can affect the degree of atomization of the one-dimensional conductive material nanowire solution, that is, the size of the droplets, and then affect the droplet evaporation rate and the relationship between capillary flow and Marangoni reflux, and ultimately affect the self-assembly behavior of the one-dimensional conductive material nanowires. As the carrier gas pressure decreases and the nozzle diameter of the spray gun increases, the mesh of the formed fishnet structure also becomes larger. This shows that the microscopic morphology and optoelectronic properties of the electrode can be adjusted through a simple strategy, showing the advantages of this method being simple and easy to control.

[0078] The spraying application method has high requirements for the surface contact angle of the substrate, requiring the surface contact angle of the substrate to be between 55 and 160.6°. The contact angle of the conventional degradable substrate is in the range of 15 to 40°. The droplets cannot be pinned and it is difficult to form a fishnet-like conductive electrode. The fishnet-like conductive electrode is achieved by adding a hydrophobic modifier to the silver nanowire solution and adjusting the air pressure, temperature and other parameters during spraying. In detail, a high ambient temperature is conducive to the formation of a fishnet-like conductive electrode, and the temperature range for forming a fishnet-like conductive electrode is 15 to 50°C. The solvent ratio requires high volatility, but too high volatility will cause the droplet to completely dry before the silver nanowires are deposited on the edge of the droplet. Spraying drives the solvent to evaporate by spraying gas to enhance the capillary force. The air pressure range is 0.01MPa to 1MPa.

[0079] Step 3: Heat the degradable substrate to completely evaporate the solvent on its surface, forming a fishnet-like conductive network.

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

[0081] Step 4: coating the degradable polymer solution on the surface of the degradable substrate having the fishnet-shaped conductive network, and then heating and curing the solution to form a flexible conductive film.

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

[0083] The method of coating the degradable polymer solution on the surface of the degradable substrate with a fishnet-like conductive network is a spin coating method, which can adjust the thickness of the flexible substrate and the flexible transparent electrode to meet the needs of different usage scenarios. The rotation speed of the spin coater is 50-1500rpm, and the spin coating time is 1-150s.

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

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

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

[0087] Example 1

[0088] (1) Select silver nanowires with a diameter and length of 30 nm and 20 um respectively and add them to methanol to prepare a silver nanowire solution with a concentration of 0.4 mg / ml, and add Xingyao Chemical's organosilicon hydrophobic modifier to the silver nanowire solution;

[0089] (2) Pick red rose petals of appropriate size (about 2 cm × 2 cm) from nature, wash them alternately with deionized water and anhydrous ethanol for 30 seconds, and blow dry the surface with nitrogen gas;

[0090] (3) The red rose petal substrate obtained in step (2) is evenly attached to the surface of a 10 cm × 2.5 cm glass slide;

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

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

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

[0094] Example 2

[0095] (1) Select silver nanowires with a diameter and length of 30 nm and 20 um respectively, add them to ethanol to prepare a silver nanowire solution with a concentration of 0.5 mg / ml, and add Red Spider BOS-04 series glass nano self-cleaning liquid to the silver nanowire solution;

[0096] (2) Pick red peony petals of appropriate size (about 3 cm × 3 cm) from nature, wash them alternately with deionized water and anhydrous ethanol for 30 seconds, and blow dry the surface with nitrogen gas.

[0097] (3) The red peony petal substrate obtained in step (2) is evenly attached to the surface of a 6 cm×6 cm glass slide;

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

[0099] (5) Control the movement speed of the spray gun to 10 cm / s, adjust the spray gun spray angle, so that the normal line of the silver nanowire liquid column is always 90° perpendicular to the tangent line of the red peony petal substrate surface, and use a constant temperature digital heating table to set the temperature to 35°C. The heating time is 0.5 h, so that the solvent on the surface of the red peony petal substrate is completely evaporated, ensuring that a fishnet-shaped conductive electrode with uniform square resistance can be formed on the surface of the red peony petal substrate. The optical microscope spectrum of the fishnet-shaped conductive electrode on the peony petal substrate is as follows: Figure 3 As shown in the figure, the fishnet-shaped conductive electrode on the peony petal substrate retains many gaps and has a high visible light transmittance. At the same time, the fishnet-shaped electrode has a clear conductive path and a low and uniform sheet resistance.

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

[0101] Example 3

[0102] (1) Selecting silver nanowires with a diameter and length of 30 nm and 20 um respectively, adding them to ethanol to prepare a silver nanowire solution with a concentration of 0.4 mg / ml; adding Namech F-6000 easy-to-clean nano-hydrophobic modifier to the silver nanowire solution;

[0103] (2) White tulip petals of appropriate size (about 2 cm × 2 cm) were picked from nature, washed alternately with deionized water and anhydrous ethanol for 30 seconds, and the surface was dried with nitrogen gas.

[0104] (3) The red peony petal substrate obtained in step (2) is evenly attached to the surface of a 10 cm×2.cm glass slide.

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

[0106] (5) The moving speed of the spray gun is controlled to be 10 cm / s, and the spraying angle of the spray gun is adjusted so that the normal line of the silver nanowire liquid column is always 90° perpendicular to the tangent line of the surface of the white tulip petal substrate, and the temperature is set to 35°C using a constant temperature digital heating table. The heating time is 0.5 h, so that the solvent on the surface of the white tulip petal substrate is completely evaporated, ensuring that a fishnet-shaped conductive electrode with uniform square resistance can be formed on the surface of the white tulip petal substrate. The optical microscope map of the fishnet-shaped conductive electrode on the tulip petal substrate is as follows: Figure 4 As shown in the figure, the fishnet-shaped conductive electrode on the tulip petal substrate retains many gaps and has a high visible light transmittance. At the same time, the fishnet-shaped electrode has a clear conductive path and a low and uniform sheet resistance.

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

[0108] Example 4

[0109] (1) Select silver nanowires with a diameter and length of 30 nm and 20 um respectively and add them to ethanol to prepare a silver nanowire solution with a concentration of 0.5 mg / ml, and add a hahne / Han Neng waterproofing agent hydrophobic modifier to the silver nanowire solution;

[0110] (2) White narcissus petals of appropriate size (about 2 cm × 2 cm) were picked from nature, washed alternately with deionized water and anhydrous ethanol for 30 seconds, and the surface was dried with nitrogen gas.

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

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

[0113] (5) The spray gun movement speed was controlled to be 10 cm / s, and the spray gun spraying angle was adjusted so that the normal line of the silver nanowire liquid column was always 90° perpendicular to the tangent line of the white narcissus petal substrate surface, and the temperature was set to 35°C using a constant temperature digital heating table. The heating time was 0.5 h, so that the solvent on the surface of the white narcissus petal substrate was completely evaporated, ensuring that a fishnet-shaped conductive electrode with uniform square resistance could be formed on the surface of the white narcissus petal substrate. The optical microscope map of the fishnet-shaped conductive electrode on the narcissus petal substrate is as follows: Figure 5 As shown in the figure, the fishnet-shaped conductive electrode on the narcissus petal substrate retains many gaps and has a high visible light transmittance. At the same time, the fishnet-shaped electrode has a clear conductive path and a low and uniform sheet resistance.

[0114] (6) A 40% polylactic acid (PLLA) solution was coated on the surface of a narcissus petal substrate having a fishnet-like conductive network. The spin coater speed was set to 400 r / min for 50 s. The substrate was then placed in an oven at 60°C for 30 min for heating and curing to form a flexible conductive film. After the degradable substrate and the flexible conductive film were cooled, they were separated to obtain a fishnet-like conductive electrode.

[0115] Example 5

[0116] (1) Select silver nanowires with a diameter and length of 30 nm and 20 um, respectively, and add them to ethanol to prepare a silver nanowire solution with a concentration of 0.4 mg / ml, and add Namech F-6000 easy-to-clean nano-hydrophobic modifier to the silver nanowire solution;

[0117] (2) Pick pink rose petals of appropriate size (about 4 cm × 4 cm) from nature, wash them alternately with deionized water and anhydrous ethanol for 30 seconds, and blow dry the surface with nitrogen gas.

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

[0119] (4) 2 ml of 0.4 mg / ml silver nanowire solution was measured by a pipette and added to a spray gun, wherein the nozzle diameter of the spray gun was 0.3 mm, the shortest distance between the nozzle and the substrate was 5 cm, the spray carrier gas was high-purity air, and the spray pressure was 0.2 MPa;

[0120] (5) The moving speed of the spray gun was controlled to be 10 cm / s, and the spraying angle of the spray gun was adjusted so that the normal line of the silver nanowire liquid column was always 90° perpendicular to the tangent line of the pink rose petal substrate surface, and the temperature was set to 35°C using a constant temperature digital heating table. The heating time was 0.5 h, so that the solvent on the surface of the pink rose petal substrate was completely evaporated, ensuring that a fishnet-shaped conductive electrode with uniform square resistance could be formed on the surface of the pink rose petal substrate. The optical microscope map of the fishnet-shaped conductive electrode on the rose petal substrate is as follows: Figure 6As shown in the figure, the fishnet-shaped conductive electrode on the rose petal substrate retains many gaps and has a high visible light transmittance. At the same time, the fishnet-shaped electrode has a clear conductive path and a low and uniform sheet resistance.

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

[0122] Example 6

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

[0124] (1) Select silver nanowires with a diameter and length of 30 nm and 20 μm respectively and add them to methanol to prepare a Ag NWs solution with a concentration of 0.5 mg / ml, and add the Xingyao Chemical organic silicon hydrophobic modifier to the Ag NWs solution;

[0125] (2) The Ag NWs solution with the Xingyao Chemical organic silicon hydrophobic modifier added was added into a spray gun with a nozzle diameter of 0.3 mm and a spray distance of 10 cm. The Ag NWs solution was sprayed on a 2 cm × 2 cm modified hackberry leaf substrate with a square resistance of about 50 Ω / sq. The solution was evaporated to form a fishnet-like conductive network.

[0126] Example 6 Optical microscope image of a fishnet-shaped conductive electrode based on a leaf substrate, such as Figure 7 shown.

[0127] Example 7

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

[0129] (1) Silver nanowires with a diameter and length of 20 nm and 30 μm, respectively, were selected and added to ethanol to prepare a Ag NWs solution with a concentration of 0.6 mg / ml. Red Spider BOS-04 series glass nano self-cleaning hydrophobic modifier was added to the Ag NWs solution.

[0130] (2) Then, the Ag NWs solution with the addition of Spider BOS-04 series glass nano self-cleaning hydrophobic modifier was added into the spray gun with a nozzle diameter of 0.5 mm and a spray distance of 15 cm. The Ag NWs solution was sprayed on a 6 cm × 6 cm base of the green radish leaf with the square resistance controlled to be about 10 Ω / sq. The solution was evaporated to form a fishnet-like conductive network.

[0131] (3) The base of the green radish leaf with a fishnet-like structure was placed on a coating machine, and the liquid polylactic acid solution was spin-coated on the base of the green radish leaf sprayed with the Ag NWs fishnet-like structure at a rotation speed of 900 rpm.

[0132] (4) The liquid polylactic acid and the green radish leaf substrate coated with the Ag NWs fishnet structure conductive network are placed in an oven and heated at 60° C. for 40 minutes, and the above structure is cured into a film.

[0133] (5) After the green radish leaf substrate and the cured flexible conductive film are cooled, the PLLA layer and the Ag NWs layer are peeled off from the green radish leaf substrate to obtain a fishnet-shaped conductive electrode.

[0134] Figure 8 It is a graph of the square resistance uniformity of the fishnet-shaped conductive electrode based on the blade substrate in Example 7 of the present invention; the electrical performance of the square resistance uniformity of the fishnet-shaped conductive electrode in Example 7 is verified, the square resistance uniformity is good, and the maximum change of square resistance is about 4%.

[0135] Example 8

[0136] In this embodiment, a fishing net-shaped conductive electrode based on a leaf substrate is provided, and the preparation method thereof is as follows:

[0137] (1) Silver nanowires with a diameter and length of 10 nm and 40 μm, respectively, were selected and added to ethanol to prepare a Ag NWs solution with a concentration of 0.4 mg / ml, and the hahne / Han Neng waterproof and hydrophobic modifier was added to the Ag NWs solution.

[0138] (2) Then, the Ag NWs solution with the addition of the hahne / Han Neng waterproof and hydrophobic modifier was added into a spray gun with a nozzle diameter of 0.6 mm and a spray distance of 18 cm. The Ag NWs solution was sprayed on a 2 cm × 2 cm sycamore leaf substrate with a square resistance of about 20 Ω / sq. The solution was evaporated to form a fishnet-like conductive network.

[0139] (3) The sycamore leaf substrate with the fishnet-like structure was placed on a coating machine, and the liquid polylactic acid solution was spin-coated on the sycamore leaf substrate sprayed with the Ag NWs fishnet-like structure at a rotation speed of 800 rpm.

[0140] (4) The liquid polylactic acid and the sycamore leaf substrate coated with the Ag NWs fishnet-like conductive network were placed in an oven and heated at 50° C. for 60 min, and the structure was cured into a film.

[0141] (5) After the paulownia leaf substrate and the cured flexible conductive film are cooled, the PLLA layer and the Ag NWs layer are peeled off from the paulownia leaf substrate to obtain a fishnet-shaped conductive electrode.

[0142] The flexible conductive film in Example 8 was immersed in deionized water, ethanol, isopropanol, methanol and acetone for 2 hours. Fig. 9 The change in square resistance is monitored to test its chemical stability.

[0143] Conductive silver paste was applied to both ends of the flexible conductive film prepared in Example 8 to increase electrical contact. After curing, a source meter was used to provide a DC voltage on both sides of the electrode to test the performance of the electric heater. Fig.10 As shown in Figure 2, the flexible transparent electric heater has good Joule heating performance. The morphology of the flexible conductive film after being immersed in NaOH (pH = 13.0) solution for different time periods is shown in Figure 2. Fig.11 As shown, it is proved that the flexible conductive film has excellent degradability.

[0144] Comparative Example

[0145] In this embodiment, a fishnet-shaped conductive electrode prepared on the surface of a glass substrate is provided. Glass is used as the substrate material, and the other preparation methods are the same as those in Embodiment 1. The obtained conductive film is as follows: Fig.12 As shown, the solidified nanosilver can only be stacked in a linear shape and the "fishnet" structure cannot be obtained, and its conductive performance is significantly reduced.

[0146] In one or more embodiments, an electronic device is provided, which uses a fishnet-shaped conductive electrode prepared by the method for preparing a fishnet-shaped 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 fishing net-shaped conductive electrode of the embodiment of the present invention is a degradable electrode, which can be used in the fields of electric heaters, electromagnetic interference shielding, sensors, smart windows, solar cells, etc.

[0148] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing a fishnet-shaped conductive electrode based on a degradable substrate, characterized in that: include: Adding a hydrophobic modifier 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; The degradable substrate is cleaned and leveled, and after the surface of the degradable substrate is dried, a one-dimensional conductive material nanowire solution with a hydrophobic modifier added thereto is vertically applied to the surface of the degradable substrate; The degradable substrate is heated to completely volatilize the solvent on its surface, thereby forming a fishnet-like conductive network; The degradable polymer solution is coated on the surface of the degradable substrate having a fishnet-shaped conductive network, and then heated and cured to form a flexible conductive film; After the degradable substrate and the flexible conductive film are cooled, the two are separated to obtain a fishnet-shaped conductive electrode.

2. The method for preparing a fishnet-shaped conductive electrode based on a degradable substrate according to claim 1, characterized in that: The degradable substrate is a petal substrate or a leaf substrate.

3. The method for preparing a fishnet-shaped conductive electrode based on a degradable substrate according to claim 1, characterized in that: The one-dimensional conductive material nanowires are silver nanowires, copper nanowires, gold nanowires or carbon nanotubes.

4. The method for preparing a fishnet-shaped conductive electrode based on a degradable substrate according to claim 1, characterized in that: When the one-dimensional conductive material 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 um.

5. The method for preparing a fishnet-shaped conductive electrode based on a degradable substrate according to claim 1, characterized in that: The one-dimensional conductive material nanowire solution is vertically applied on the surface of the degradable substrate by spraying, dripping or spin coating.

6. The method for preparing a fishnet-shaped conductive electrode based on a degradable substrate according to claim 1, characterized in that: The one-dimensional conductive material nanowire solution is applied on the surface of the degradable substrate at least once.

7. The method for preparing a fishnet-shaped conductive electrode based on a degradable substrate according to claim 6, characterized in that: When the number of times of applying the one-dimensional conductive material nanowire solution on 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 dried.

8. The method for preparing a fishnet-shaped conductive electrode based on a degradable substrate according to claim 1, characterized in that: The temperature at which the degradable substrate is heated is 50° C., the heating time is 30 s, and the number of cycles of applying the hydrophobic modification solution is 3 times.

9. The method for preparing a fishnet-shaped conductive electrode based on a degradable substrate according to claim 1, characterized in that: The degradable polymer solution is coated on the surface of the degradable substrate with a fishnet-shaped conductive network by a spin coating method.

10. An electronic device, characterized in that: The invention comprises a fishnet-shaped conductive electrode prepared by the method for preparing a fishnet-shaped conductive electrode based on a degradable substrate as described in any one of claims 1 to 9.

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