Composite flexible transparent electrode, and preparation method therefor and use thereof

Abstract

The present application relates to the technical field of flexible materials, and provides a composite flexible transparent electrode, and a preparation method therefor and a use thereof. The composite flexible transparent electrode provided in the present application comprises a fiber fabric reinforced resin highly light-transmitting substrate and a conductive coating. The fiber fabric reinforced resin highly light-transmitting substrate comprises a light-transmitting resin matrix and a light-transmitting fiber fabric distributed in the light-transmitting resin matrix. In the present application, the light-transmitting fiber fabric is used as a reinforcing material, so that the fiber fabric reinforced resin highly light-transmitting substrate has excellent mechanical strength; and the conductive coating is provided on this basis, so that the obtained composite flexible transparent electrode has excellent mechanical strength and weather resistance while having good light transmitting performance and conductivity. The present application has broad prospects for application in flexible optoelectronic devices such as flexible photovoltaic devices.

Description

A composite flexible transparent electrode, its preparation method and application

[0001] This application claims priority to Chinese Patent Application No. CN202411958604.7, filed on December 30, 2024, entitled "A Composite Flexible Transparent Electrode and Its Preparation Method and Application", the entire contents of which are incorporated herein by reference. Technical Field

[0002] This application relates to the field of flexible materials technology, and in particular to a composite flexible transparent electrode, its preparation method, and its application. Background Technology

[0003] Flexible electronics technology represents a revolutionary advancement in electronics, attracting widespread global attention and experiencing rapid development. Furthermore, the increasing prevalence of new energy vehicles, particularly the integration of solar panels on vehicle roofs as a new source of supplemental power, has spurred demand for lightweight, flexible, and shock-resistant photovoltaic modules. Flexible photovoltaic devices made from thin-film batteries have also provided solutions for many outdoor products. Therefore, flexible photovoltaic devices will be crucial for developing fully flexible self-powered electronic products, large-scale building-integrated photovoltaics (BIPV), wearable photovoltaics, automotive photovoltaics, and aerospace applications.

[0004] Flexible transparent electrodes (FTEs) are a core component of flexible photovoltaic devices. They need to possess both optical transparency and conductivity. For example, their light transmittance typically requires a transmittance of over 80% for a visible light source at 550nm, and their conductivity requires a surface impedance below 1000Ω / sq. They also need good mechanical strength. Currently, the key performance characteristics of flexible transparent electrodes mainly depend on the flexible substrate supporting the conductive material. Good substrate flexibility can simultaneously improve the photoelectric and mechanical properties of the device.

[0005] Currently, flexible substrates are typically made of metal or plastic. Metal substrates are mainly formed from titanium foil, copper foil, or stainless steel foil, offering good thermal stability, high electrical conductivity, and high corrosion resistance. However, their disadvantage is low light transmittance, which affects the light absorption characteristics of the device. Plastic substrates are mainly formed from polymer materials such as polyvinyl alcohol (PVA), polyester (PET), polyimide (PI), or polyethylene naphthalate (PEN), offering advantages such as high optical transparency and high flexibility. However, their mechanical strength and weather resistance are relatively poor. Summary of the Invention

[0006] The purpose of this application is to provide a composite flexible transparent electrode, its preparation method and application. The composite flexible transparent electrode provided by this application has good light transmittance and conductivity, as well as excellent mechanical strength and weather resistance.

[0007] To achieve the above-mentioned objectives, this application provides the following technical solution:

[0008] This application provides a composite flexible transparent electrode, comprising a fiber fabric reinforced resin high-transmittance substrate and a conductive coating stacked together. The fiber fabric reinforced resin high-transmittance substrate includes a light-transmitting resin matrix and light-transmitting fiber fabric distributed in the light-transmitting resin matrix.

[0009] Preferably, the thickness of the fiber-reinforced resin high-transmittance substrate is 100–300 μm; and the thickness of the conductive coating is 20–1000 nm.

[0010] Preferably, the raw materials for preparing the translucent resin matrix include 100 parts of translucent acrylic resin, 0.1 to 10 parts of toughening agent, and 0.3 to 10 parts of nanofiller, by mass percentage; the mass ratio of the translucent resin matrix to the translucent fiber fabric is 1 to 10:1.

[0011] Preferably, the toughening agent comprises low-density polyethylene powder, MOUSSEX S 667, MOUSSEX SF 561, or... COC 6013F-4.

[0012] Preferably, the low-density polyethylene powder includes LDPE 500026 or LDPE 200024.

[0013] Preferably, the nanofiller includes one or more of fumed silica, fumed alumina, nanocellulose, and nanobarium oxide.

[0014] Preferably, the raw materials for preparing the translucent resin matrix further include 0.1 to 5 parts of an internal release agent.

[0015] Preferably, the internal release agent is LubeKote 6802.

[0016] Preferably, the fibers in the translucent fiber fabric include one or more of glass fibers, carbon fibers, and basalt fibers; the basis weight of the translucent fiber fabric is 20–100 g / m². 2 .

[0017] Preferably, under light wavelength conditions of 400–1100 nm, the light transmittance of the fiber-reinforced resin high-transmittance substrate is 80–92.8%.

[0018] Preferably, the method for preparing the fiber-reinforced resin high-transmittance substrate includes the following steps:

[0019] The raw materials for preparing the translucent resin matrix are mixed to obtain a mixed powder;

[0020] The mixed powder is spread on the surface of a light-transmitting fiber fabric and laminated to obtain the fiber fabric-reinforced resin high-transmittance substrate.

[0021] Preferably, the lamination process further includes venting; the venting includes sequentially increasing pressure, holding pressure, and decreasing pressure; the number of venting operations is 1 to 5, the holding pressure during each venting operation is 0.5 to 3 MPa, and the holding time is 5 to 15 minutes; the venting is performed at room temperature.

[0022] Preferably, the lamination pressure is 0.1 to 3 MPa; the lamination adopts a programmed temperature rise, and the specific temperature rise program includes: rising from room temperature to a first holding temperature at a first heating rate and performing a first holding, then rising to a second holding temperature at a second heating rate and performing a second holding, then rising to a third holding temperature at a third heating rate and performing a third holding, and then rising to a fourth holding temperature at a fourth heating rate and performing a fourth holding.

[0023] The first heating rate, the second heating rate, and the third heating rate are each independently 3–10 °C / min, and the fourth heating rate is 3–5 °C / min; the first holding temperature is 30–50 °C, and the first holding time is 5–20 min; the second holding temperature is 70–100 °C, and the second holding time is 1–10 min; the third holding temperature is 110–130 °C, and the third holding time is 5–20 min; the fourth holding temperature is 140–170 °C, and the fourth holding time is 15–60 min.

[0024] Preferably, a surface treatment agent is distributed on the surface of the fiber fabric reinforced resin high-transmittance substrate that is in contact with the conductive coating. When the surface treatment agent is distributed on the fiber fabric reinforced resin high-transmittance substrate, the lamination process further includes: using the surface treatment agent to smooth the surface of the composite film obtained after lamination that is to be in contact with the conductive coating, thereby obtaining the fiber fabric reinforced resin high-transmittance substrate.

[0025] Preferably, the surface treatment agent includes liquid paraffin, polymethyl methacrylate, polydimethylsiloxane, or polyimide.

[0026] Preferably, the planarization process includes: applying a surface treatment agent to the surface of the laminated composite film to be in contact with the conductive coating, and then performing heat treatment for strengthening.

[0027] Preferably, the thickness of the surface treatment agent coating formed by the surface treatment agent is 0.2 to 3 μm.

[0028] Preferably, the heat treatment strengthening temperature is 70–140°C, and the time is 1–24 h.

[0029] Preferably, the conductive material used in the conductive coating includes one or more of indium tin oxide, silver nanowires, and carbon nanomaterials.

[0030] Preferably, the composition of the indium tin oxide is based on indium oxide and tin oxide, and the molar ratio of indium oxide to tin oxide is 9:1.

[0031] Preferably, the silver nanowires have a length of 5–300 μm and a diameter of 20–200 nm.

[0032] Preferably, the carbon nanomaterial includes graphene and / or carbon nanotubes; the thickness of the graphene sheets is 0.4–10 nm; and the diameter of the carbon nanotubes is 2–100 nm.

[0033] This application provides a method for preparing the composite flexible transparent electrode described in the above technical solution, including the following steps:

[0034] A conductive coating is prepared on one side of a fiber-reinforced resin high-transmittance substrate to obtain the composite flexible transparent electrode.

[0035] Preferably, when the conductive material used in the conductive coating is indium tin oxide, the conductive coating is prepared by magnetron sputtering.

[0036] Preferably, the magnetron sputtering method includes DC sputtering, medium-frequency magnetron sputtering, double-click magnetron sputtering, or plasma-enhanced magnetron sputtering.

[0037] Preferably, the magnetron sputtering method includes sequential sputtering and annealing;

[0038] The sputtering conditions include: a target-to-substrate distance of 5–10 cm and a background vacuum of 2.0 × 10⁻⁶. -3 Below Pa, the sputtering current is 0.5–0.7 A, the sputtering voltage is 300–500 V, the substrate bias voltage is -200 V to 0 V, the sputtering power is 100–500 W, the sputtering gas pressure is 0.1–2.5 Pa, the argon flow rate is 10–20 sccm, the oxygen flow rate is 0–2 sccm, the substrate temperature is 110–170 °C, and the sputtering time is 30–60 s;

[0039] The annealing conditions include: a temperature of 170–200°C and a holding time of 1–5 min; the annealing is carried out under vacuum conditions.

[0040] Preferably, when the conductive material used in the conductive coating is silver nanowires, the conductive coating is prepared on one side of the fiber-reinforced resin high-transmittance substrate using a wet process, including the following steps:

[0041] Silver nanowires were dispersed in an alcohol solvent to obtain a silver nanowire dispersion; the silver nanowire dispersion was coated on one side of the fiber-reinforced resin high-transmittance substrate, dried, and then pressed to obtain the composite flexible transparent electrode.

[0042] Preferably, the alcohol solvent includes ethanol and / or isopropanol, and the concentration of the silver nanowire dispersion is 4–20 mg / mL; the coating is spin coating, and each spin coating includes sequential low-speed spin coating and high-speed spin coating, wherein the rotation speed of each low-speed spin coating is 500–3000 rpm and the time is 10–120 s; the rotation speed of each high-speed spin coating is 3000–6000 rpm and the time is 5–60 s; the pressing pressure is 5–25 MPa and the holding time is 10–60 s.

[0043] Preferably, when the conductive material used in the conductive coating is carbon nanomaterial, the method for preparing the conductive coating includes the following steps: mixing carbon nanomaterial, dispersant and solvent to obtain carbon nanomaterial dispersion; coating the carbon nanomaterial dispersion on one side of the fiber fabric reinforced resin high-transmittance substrate, drying and washing to remove the dispersant, and then heat-treating to obtain the composite flexible transparent electrode.

[0044] Preferably, the dispersant is sodium dodecyl sulfate, the solvent is water and / or alcohol, the concentration of carbon nanomaterials in the carbon nanomaterial dispersion is 0.1-1.5 wt%, the coating is spraying, and the heat treatment temperature is 30-70°C, with a holding time of 30-120 min.

[0045] This application provides the application of the composite flexible transparent electrode described in the above technical solution or the composite flexible transparent electrode prepared by the preparation method described in the above technical solution in flexible electronic devices.

[0046] Preferably, the flexible electronic device includes a flexible optoelectronic device, a flexible sensor, or a flexible display; the flexible optoelectronic device includes a flexible photovoltaic device, a flexible organic light-emitting semiconductor, a flexible photon receiver, or a flexible optical communication device; the flexible photovoltaic device includes a flexible perovskite solar cell, a flexible silicon thin-film solar cell, a flexible silicon-perovskite solar cell, a flexible copper indium gallium selenide thin-film solar cell, a flexible cadmium telluride solar cell, or a flexible organic solar cell.

[0047] The present invention provides a flexible electronic device, including the composite flexible transparent electrode described in the above technical solution or the composite flexible transparent electrode prepared by the preparation method described in the above technical solution.

[0048] This application provides a composite flexible transparent electrode, comprising a fiber-reinforced resin high-transmittance substrate and a conductive coating stacked together. The fiber-reinforced resin high-transmittance substrate includes a light-transmitting resin matrix and light-transmitting fiber fabric distributed within the light-transmitting resin matrix. This application uses light-transmitting fiber fabric as the reinforcing material, giving the fiber-reinforced resin high-transmittance substrate excellent mechanical strength. The conductive coating further enhances this, resulting in a composite flexible transparent electrode that possesses good light transmittance and conductivity, as well as excellent mechanical strength and weather resistance, making it promising for applications in flexible optoelectronic devices such as flexible photovoltaic devices. Detailed Implementation

[0049] This application provides a composite flexible transparent electrode, comprising a fiber fabric reinforced resin high-transmittance substrate and a conductive coating stacked together. The fiber fabric reinforced resin high-transmittance substrate includes a light-transmitting resin matrix and light-transmitting fiber fabric distributed in the light-transmitting resin matrix.

[0050] The composite flexible transparent electrode provided in this application includes a conductive coating. As one embodiment of this application, the thickness of the conductive coating can be 20-1000 nm, specifically 20 nm, 50 nm, 75 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 500 nm, 750 nm, or 1000 nm. As one embodiment of this application, the conductive material used in the conductive coating may include one or more of indium tin oxide, silver nanowires, and carbon nanomaterials, specifically indium tin oxide, silver nanowires, or carbon nanomaterials; the composition of the indium tin oxide is based on indium oxide (In2O3) and tin oxide (SnO2), and the molar ratio of indium oxide to tin oxide may be 9:1; the length of the silver nanowires may be 5–300 μm, and the diameter may be 20–200 nm; the carbon nanomaterials may include graphene and / or carbon nanotubes, specifically graphene or carbon nanotubes, wherein the thickness of the graphene sheets may be 0.4–10 nm (i.e., including single-layer graphene sheets and multi-layer graphene sheets), and the radial dimension is not particularly limited; the diameter of the carbon nanotubes may be 2–100 nm, and the length is in the micrometer range, with no particular limitation on the specific length dimension.

[0051] The composite flexible transparent electrode provided in this application includes a fiber-reinforced resin high-transmittance substrate stacked with the conductive coating. As one embodiment of this application, the thickness of the fiber-reinforced resin high-transmittance substrate can be 100–300 μm, specifically 100 μm, 120 μm, 140 μm, 160 μm, 180 μm, 200 μm, 220 μm, 240 μm, 260 μm, 280 μm, or 300 μm. As one embodiment of this application, the transmittance of the fiber-reinforced resin high-transmittance substrate is 80–92.8%, specifically 80%, 82%, 85%, 87%, 89%, 90%, 91%, 92%, or 92.8%; in this invention, the transmittance of the fiber-reinforced resin high-transmittance substrate is tested under light wavelength conditions of 400–1100 nm.

[0052] The fiber-reinforced resin high-transmittance substrate described in this application includes a translucent resin matrix and a translucent fiber fabric distributed within the translucent resin matrix. As one embodiment of this application, the mass ratio of the translucent resin matrix to the translucent fiber fabric can be 1 to 10:1, specifically 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, or 10:1. As one embodiment of this application, the fibers in the translucent fiber fabric can include one or more of glass fibers, carbon fibers, and basalt fibers, specifically glass fibers (i.e., glass fiber), carbon fibers (i.e., carbon fiber), or basalt fibers; the basis weight of the translucent fiber fabric can be 20 to 100 g / m³. 2 Specifically, it can be 20g / m 2 30g / m 2 40g / m 2 50g / m 2 60g / m 2 70g / m 2 80g / m 2 90g / m 2 Or 100g / m 2 In the embodiments of this application, the composite flexible transparent electrode is specifically prepared using low-dielectric cross-ribbed glass fiber cloth (the dielectric constant can be 3 to 8, specifically 3, 4, 5, 6, 7 or 8), purchased from Shanghai Tianhuan Materials Technology Co., Ltd., and the model can be HL2116, HL1080, HL106, HL1037 or ultra-thin electronic-grade glass fiber cloth 1027, 1017, etc.

[0053] In one embodiment of this application, the raw materials for preparing the translucent resin matrix, by weight, include 100 parts of translucent acrylic resin, 0.1 to 10 parts of toughening agent, and 0.3 to 10 parts of nanofiller. The raw materials for preparing the translucent resin matrix are described in detail below.

[0054] In one embodiment of this application, the raw materials for preparing the translucent resin matrix, by weight, include 100 parts of translucent acrylic resin. In another embodiment of this application, the translucent acrylic resin is prepared from raw materials comprising the following parts by weight: 100 parts solvent, 0.3-1 parts methacrylic acid, 10-30 parts methyl methacrylate, 15-20 parts n-butyl methacrylate, 10-25 parts glycidyl methacrylate, 2-5 parts functional monomer, 10-20 parts styrene, 1-4 parts chain transfer agent, and 1-5 parts initiator; the functional monomer includes one or more of hexafluorobutyl methacrylate, n-dodecyl acrylate, and polyethylene glycol methacrylate. In one embodiment of this application, the chain transfer agent includes one or more of n-dodecyl mercaptan, tert-dodecyl mercaptan, and tert-nonyl mercaptan; the initiator includes one or more of di-tert-butyl peroxide, benzoyl peroxide, dicumyl peroxide, and tert-butylperoxide-3,5,5-trimethylhexanoate; the solvent is one or more of ethylene glycol ethyl ether acetate, toluene, xylene, ethylene glycol butyl ether, and methyl isobutyl ketone; the refractive index of the transparent acrylic resin is 1.52-1.55. In another embodiment of this application, the preparation method of the transparent acrylic resin includes the following steps: heating and mixing solvent, methacrylic acid, methyl methacrylate, n-butyl methacrylate, glycidyl methacrylate, functional monomer, styrene, and initiator; adding the chain transfer agent; and carrying out a polymerization reaction to obtain the transparent acrylic resin; the polymerization reaction temperature can be 140-180°C, and the time can be 1-4 hours; after the polymerization reaction, vacuum distillation is preferably performed, and the melt obtained after vacuum distillation is taken out and cooled to obtain the transparent acrylic resin. In this embodiment, the transparent acrylic resin is specifically prepared according to Chinese Patent Application No. 202410666891.8. Using the aforementioned type of transparent acrylic resin in this embodiment can increase the visible light transmittance and weather resistance of the fiber-reinforced resin high-transmittance substrate, which is beneficial for improving the photoelectric efficiency of flexible optoelectronic devices, expanding the application scenarios of the devices, and extending their service life.

[0055] As one embodiment of this application, based on the mass fraction of the translucent acrylic resin, the raw materials for preparing the translucent resin matrix of this application include 0.1 to 10 parts of toughening agent, specifically 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 parts. As one embodiment of this application, the toughening agent may include low-density polyethylene powder, MOUSSEX S 667, MOUSSEX SF 561, or... COC 6013F-4; the low-density polyethylene powder includes LDPE 500026 or LDPE 200024; in this embodiment, LDPE 500026 and LDPE 200024 are specifically purchased from SABIC, and MOUSSEX S 667 and MOUSSEX SF 561 are specifically purchased from Changzhou Tianhe International Trade Co., Ltd. COC 6013F-4 was specifically purchased from Polyplastics Co., Ltd., Japan. The toughening agent of the above type used in the embodiments of this application can significantly reduce defects such as bubbles, pinholes, and microcracks caused by the polymerization reaction in fiber-reinforced resin high-transmittance substrates, thereby improving their appearance, reducing surface roughness, enhancing surface smoothness, and improving barrier properties; it also helps to improve the quality and electrical properties of conductive coatings.

[0056] As one embodiment of this application, based on the mass fraction of the translucent acrylic resin, the raw materials for preparing the translucent resin matrix of this application include 0.3 to 10 parts of nanofiller, specifically 0.3 parts, 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, or 10 parts. As one embodiment of this application, the nanofiller may include one or more of fumed silica, fumed alumina, nanocellulose, and nanobarium oxide, specifically fumed silica, fumed alumina, nanocellulose, or nanobarium oxide. In this embodiment, the fumed silica is specifically purchased from Evonik Industries AG, model AEROSIL R972; the fumed alumina is purchased from Hubei Huifu Nanomaterials Co., Ltd., model ALUNA-100; and the nanobarium oxide is purchased from Wuhan Jiyesheng Chemical Co., Ltd. The above-mentioned nanofillers used in the embodiments of this application can improve the tensile strength of the fiber fabric reinforced resin high-transmittance substrate, reduce the thermal shrinkage rate, improve the impact strength, improve the high temperature resistance, enhance the barrier properties, give it excellent mechanical properties, and reduce the permeability of small molecules such as oxygen and water vapor.

[0057] As one embodiment of this application, based on the mass fraction of the translucent acrylic resin, the raw materials for preparing the translucent resin matrix of this application may further include 0.1 to 5 parts of an internal release agent, specifically 0.1, 0.3, 0.5, 1, 2, 3, 4, or 5 parts. As one embodiment of this application, the internal release agent may be LubeKote 6802; in this embodiment, LubeKote 6802 is specifically purchased from Shanghai Lerui Curing Technology Co., Ltd.

[0058] As one embodiment of this application, the method for preparing the fiber-reinforced resin high-transmittance substrate may include the following steps:

[0059] The raw materials for preparing the translucent resin matrix are mixed to obtain a mixed powder;

[0060] The mixed powder is spread on the surface of a light-transmitting fiber fabric and laminated to obtain the fiber fabric-reinforced resin high-transmittance substrate.

[0061] This application mixes the raw materials for preparing a translucent resin matrix to obtain a mixed powder. This application does not specifically limit the mixing method, as long as the components are mixed evenly; for example, it can be internal extrusion or external mixing. In this embodiment, the raw materials for preparing the translucent resin matrix are placed in a twin-screw internal extruder for internal extrusion mixing. As one embodiment of this application, the mixture further includes pulverization; specifically, the pulverized material can be passed through a 1000-mesh sieve, and the undersize material is collected as the mixed powder.

[0062] After obtaining the mixed powder, this application spreads the mixed powder onto the surface of a translucent fiber fabric and laminates it to obtain a fiber fabric-reinforced resin high-transparency substrate. As one embodiment of this application, the translucent fiber fabric is cut to the required size according to the mass ratio of the mixed powder to the translucent fiber fabric. Then, a first release paper is laid in a lower mold, and the translucent fiber fabric is laid on the surface of the first release paper (a blank area is left at the edge of the lower mold to facilitate sufficient resin flow after heating). The mixed powder is then spread onto the surface of the translucent fiber fabric (covering the entire upper surface of the translucent fiber fabric), and a second release paper is laid on top of the mixed powder. The mold is then covered on the second release paper, and the entire assembly is transferred to a laminator for lamination. As one embodiment of this application, the first and second release papers are specifically ultra-low roughness release papers (Ra = 10–40 nm); the mold (including an upper mold and a lower mold) is specifically an ultra-smooth, ultra-clean mold well-known in the art. This application does not impose any special limitations on the specific operation method and conditions for spreading, as long as the uniform spreading of the mixed powder can be achieved.

[0063] As one embodiment of this application, the lamination process further includes venting; the venting includes sequentially increasing pressure, holding pressure, and decreasing pressure, and the number of venting operations can be 1 to 5 times, specifically 1, 2, 3, 4, or 5 times; the holding pressure during each venting operation is 0.5 to 3 MPa, specifically 0.5 MPa, 1 MPa, 2 MPa, or 3 MPa; the holding time can be 5 to 15 minutes, specifically 5 minutes, 10 minutes, or 15 minutes; the venting can be performed at room temperature. In one embodiment of this application, the lamination employs a programmed temperature rise process. The specific temperature rise process includes: raising the temperature from room temperature to a first holding temperature at a first heating rate and holding it at that temperature; raising the temperature to a second holding temperature at a second heating rate and holding it at that temperature; raising the temperature to a third holding temperature at a third heating rate and holding it at that temperature; and then raising the temperature to a fourth holding temperature at a fourth heating rate and holding it at that temperature. The first, second, and third heating rates can each be independently 3–10 °C / min, specifically 3 °C / min, 5 °C / min, 7 °C / min, or 10 °C / min. The fourth heating rate can be 3–5 °C / min, specifically 3 °C / min, 4 °C / min, or 5 °C / min. The first holding temperature can be 30–50 °C, specifically 30 °C, 35 °C, 40 °C, 45 °C, or 50 °C. The first holding time can be 5–20 min, specifically 5 min, 10 min, 20 min, 30 min, 40 min, 45 °C, or 50 °C. The second heat preservation temperature can be 70-100℃, specifically 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, or 100℃, and the second heat preservation time can be 1-10min, specifically 1min, 3min, 5min, 7min, or 10min; the third heat preservation temperature can be 110-130℃, specifically 110℃, 115℃, 120℃, 125℃, or 130℃, and the third heat preservation time can be 5-20min, specifically 5min, 10min, 15min, or 20min; the fourth heat preservation temperature can be 140-170℃, specifically 140℃, 145℃, 150℃, 155℃, 160℃, 165℃, or 170℃, and the fourth heat preservation time can be 15-60min, specifically 15min, 30min, 45min, or 60min. As one embodiment of this application, the lamination pressure can be 0.1 to 3 MPa, specifically 0.1 MPa, 0.2 MPa, 0.3 MPa, 0.4 MPa, 0.5 MPa, 1 MPa, 2 MPa or 3 MPa; that is, the pressure is kept within the above range throughout the entire temperature rise process.In one embodiment of this application, after completing the above-described heating process, cooling is further included. Specifically, the temperature is reduced to room temperature (25°C) at a rate of 5–20°C / min. The cooling rate can be 5°C / min, 10°C / min, 15°C / min, or 20°C / min. During the cooling process, the pressure is maintained at 1–10 MPa, specifically 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, or 10 MPa, and the pressure holding time can be 5–30 min, specifically 5 min, 7.5 min, 10 min, 15 min, 20 min, or 30 min. In this embodiment, lamination is performed under the above conditions, ensuring that the mixed powder is fully adsorbed onto the surface of the translucent fiber fabric and that the resin fully wets the translucent fiber fabric in a low-viscosity state and before the cross-linking and curing reaction. This facilitates interface-free composite between the resin and the translucent fiber fabric, better leveraging the mechanical reinforcement effect of the translucent fiber fabric. After lamination, the mold is removed to obtain the fiber fabric-reinforced resin high-transparency substrate.

[0064] As one embodiment of this application, according to the surface roughness requirements of the conductive coating on the fiber-reinforced resin high-transmittance substrate, a surface treatment agent may also be distributed on the surface of the fiber-reinforced resin high-transmittance substrate that contacts the conductive coating. The surface treatment agent may include liquid paraffin, polymethyl methacrylate, polydimethylsiloxane, or polyimide. When the surface treatment agent is distributed on the fiber-reinforced resin high-transmittance substrate, the lamination process further includes: using the surface treatment agent to smooth the surface of the composite film obtained after lamination that is to contact the conductive coating, thereby obtaining the fiber-reinforced resin high-transmittance substrate (also referred to as a smoothed fiber-reinforced resin high-transmittance substrate). As one embodiment of this application, the planarization process specifically includes: coating the surface of the composite film obtained after lamination with a surface treatment agent (such as liquid paraffin, polymethyl methacrylate, polydimethylsiloxane, or polyimide) to be in contact with the conductive coating, and then performing heat treatment to strengthen it, thereby obtaining the fiber fabric reinforced resin high-transmittance substrate; the temperature of the heat treatment strengthening can be 70 to 140°C, specifically 70°C, 75°C, 80°C, 90°C, 100°C, 120°C, or 140°C; the time can be 1 to 24 hours, specifically 1 hour, 5 hours, 10 hours, 15 hours, 20 hours, or 24 hours. In this embodiment, the laminated composite film is placed on a heating plate, and the temperature of the heating plate is set to 70–140°C. A surface treatment agent is placed at the center of the composite film. After the surface treatment agent has completely melted and spread, a coating stick is used to evenly spread the surface treatment agent to form a surface treatment agent coating (thickness 0.2–3 μm, specifically 0.2 μm, 0.5 μm, 1 μm, 1.5 μm, 2 μm, or 3 μm). The composite film coated with the surface treatment agent coating is then... The membrane is placed in a mold (a mold for pressing membranes in the same layer), and the pressure is set to 0.1-0.5 MPa (specifically, it can be 0.1 MPa, 0.2 MPa, 0.3 MPa, 0.4 MPa or 0.5 MPa) and maintained for 1-24 hours (specifically, it can be 1 hour, 3 hours, 5 hours, 10 hours, 15 hours, 20 hours or 24 hours) to remove gas and excess surface treatment agent and achieve heat treatment strengthening. After that, heating is stopped, and after cooling to room temperature, the mold is removed to obtain the fiber fabric reinforced resin high light transmittance substrate.

[0065] This application provides a method for preparing the composite flexible transparent electrode described in the above technical solution, including the following steps:

[0066] A conductive coating is prepared on one side of a fiber-reinforced resin high-transmittance substrate to obtain the composite flexible transparent electrode.

[0067] In one embodiment of this application, the fiber-reinforced resin high-transmittance substrate undergoes pretreatment before use. Specifically, the surface of the fiber-reinforced resin high-transmittance substrate is wiped with anhydrous ethanol and then purged with high-purity nitrogen. The specific preparation method can be selected according to the conductive material used in the conductive coating, which will be described in detail below.

[0068] In one embodiment of this application, when the conductive material is indium tin oxide (ITO), a conductive coating can be prepared on one side of the fiber-reinforced resin high-transmittance substrate using magnetron sputtering. The preparation of the conductive coating using magnetron sputtering specifically includes sequential sputtering and annealing. In one embodiment of this application, the sputtering conditions include: a target-substrate distance of 5–10 cm, specifically 5 cm, 6 cm, 7 cm, 8 cm, 9 cm, or 10 cm; and a base vacuum of 2.0 × 10⁻⁶. -3 Below Pa, specifically 1×10 -4 The sputtering current can be 0.5–0.7 A, specifically 0.5 A, 0.6 A, or 0.7 A; the sputtering voltage can be 300–500 V, specifically 300 V, 350 V, 400 V, 450 V, or 500 V; the substrate bias voltage can be -200 V to 0 V, specifically 0 V, -50 V, -100 V, -150 V, or -200 V; the sputtering power can be 100–500 W, specifically 100 W, 150 W, 200 W, 300 W, 350 W, or 500 W; the sputtering gas pressure can be 0.1–2.5 Pa, specifically 0.1 Pa or 0.5 Pa. The pressure can be 1 Pa, 1.5 Pa, 2 Pa, or 2.5 Pa; the argon flow rate can be 10–20 sccm, specifically 10 sccm, 13 sccm, 15 sccm, 17 sccm, or 20 sccm; the oxygen flow rate can be 0–2 sccm, specifically 0 sccm, 0.5 sccm, 1 sccm, 1.5 sccm, or 2 sccm; the substrate temperature can be 110–170℃, specifically 110℃, 120℃, 130℃, 150℃, or 170℃; the sputtering time can be 30–60 s, specifically 30 s, 40 s, 50 s, 55 s, or 60 s. As one embodiment of this application, the annealing conditions include: a temperature of 170–200°C, specifically 170°C, 180°C, 190°C, 195°C, or 200°C; a holding time of 1–5 minutes, specifically 1 minute, 2 minutes, 3 minutes, 4 minutes, or 5 minutes; and the annealing is performed under vacuum conditions, specifically a vacuum degree of 1 × 10⁻⁶. -3Pa. In one embodiment of this application, the argon gas is specifically high-purity argon gas (99.99%), and the oxygen gas is specifically high-purity oxygen gas (99.99%). In another embodiment of this application, the magnetron sputtering method may include DC sputtering, medium-frequency magnetron sputtering, double-click magnetron sputtering, or plasma-enhanced magnetron sputtering. In this embodiment, taking DC sputtering as an example, the magnetron sample chamber of the magnetron sputtering equipment is opened, a fiber-reinforced resin high-transmittance substrate is placed on the sample stage, an indium tin oxide target (In2O3 to SnO2 molar ratio of 9:1) is installed at the DC source target position, and sputtering is performed according to the aforementioned sputtering conditions to form an indium tin oxide coating on the surface of the fiber-reinforced resin high-transmittance substrate. After sputtering, the vacuum is released, the obtained sample film is taken out and placed in the annealing sample chamber of the magnetron sputtering equipment, and annealed according to the aforementioned annealing conditions to obtain a composite flexible transparent electrode.

[0069] In one embodiment of this application, when the conductive material is silver nanowires, a conductive coating can be prepared on one side of the fiber-reinforced resin high-transmittance substrate using a wet process, comprising the following steps: dispersing silver nanowires in an alcohol solvent to obtain a silver nanowire dispersion; coating the silver nanowire dispersion on one side of the fiber-reinforced resin high-transmittance substrate, drying, and then pressing to obtain the composite flexible transparent electrode. In another embodiment of this application, the alcohol solvent may include ethanol and / or isopropanol, and the concentration of the silver nanowire dispersion may be 4–20 mg / mL, specifically 4 mg / mL, 5 mg / mL, 6 mg / mL, 7 mg / mL, 8 mg / mL, 9 mg / mL, 10 mg / mL, 15 mg / mL, or 20 mg / mL. In one embodiment of this application, the coating method can be spin coating, and the number of spin coating cycles is determined according to the desired conductive coating thickness. Each spin coating cycle includes sequential low-speed spin coating and high-speed spin coating. Low-speed spin coating allows the silver nanowire dispersion to be evenly dispersed, while high-speed spin coating forms a dense silver nanowire network. The rotation speed of each low-speed spin coating cycle can be 500–3000 rpm, specifically 500 rpm, 600 rpm, 700 rpm, 800 rpm, or 1000 rpm. The rotation speed can be 1500rpm, 2000rpm, or 3000rpm, and the time can be 10 to 120s, specifically 10s, 15s, 30s, 45s, 60s, 90s, or 120s; the rotation speed for each high-speed spin coating can be 3000 to 6000rpm, specifically 3000rpm, 4000rpm, 5000rpm, or 6000rpm, and the time can be 5 to 60s, specifically 5s, 10s, 15s, 30s, 45s, or 60s. As one embodiment of this application, the drying temperature can be 120-220℃, specifically 120℃, 140℃, 160℃, 180℃, 200℃ or 220℃, and the time can be 0.5-3h, specifically 0.5h, 1h, 1.5h, 2h or 3h; the pressing pressure can be 5-25MPa, specifically 5MPa, 10MPa, 15MPa, 20MPa or 25MPa, and the time can be 10-60s, specifically 10s, 20s, 30s, 45s or 60s.

[0070] As one embodiment of this application, when the conductive material is carbon nanomaterial, the method for preparing a conductive coating on one side of the fiber fabric reinforced resin high-transmittance substrate includes the following steps: mixing carbon nanomaterial, dispersant and solvent to obtain a carbon nanomaterial dispersion; coating the carbon nanomaterial dispersion on one side of the fiber fabric reinforced resin high-transmittance substrate, drying and washing to remove the dispersant, and then heat-treating to obtain the composite flexible transparent electrode. In one embodiment of this application, the dispersant may be sodium dodecyl sulfate (SDS), and the solvent may be water and / or an alcohol solvent, wherein the alcohol solvent may include ethanol and / or isopropanol. In this embodiment, the solvent is specifically water and ethanol, and the volume ratio of water to ethanol may be 1:1. The concentration of carbon nanomaterials in the carbon nanomaterial dispersion may be 0.1–1.5 wt%, specifically 0.1 wt%, 0.3 wt%, 0.5 wt%, 1 wt%, or 1.5 wt%. The concentration of the dispersant in the carbon nanomaterial dispersion may be 1–10 wt%, specifically 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, or 9 wt%. As one embodiment of this application, the coating method can be spraying. Specifically, the carbon nanomaterial dispersion is loaded into a spray gun, the distance between the spray gun nozzle and the fiber fabric reinforced resin high-transmittance substrate is set to 15-30 cm, and the spray gun switch is turned on to uniformly spray the carbon nanomaterial dispersion onto one side of the fiber fabric reinforced resin high-transmittance substrate. In one embodiment of this application, the drying temperature can be 50–120°C, specifically 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, or 120°C, and the time can be 0.5–6 hours, specifically 0.5 hours, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, or 6 hours; the washing reagent can be nitric acid, and the volume fraction of the nitric acid can be 50–70%, specifically 50%, 60%, or 70%; the heat treatment temperature can be 30–70°C, specifically 30°C, 40°C, 50°C, 60°C, or 70°C, and the time can be 30–120 minutes, specifically 30 minutes, 45 minutes, 60 minutes, 90 minutes, or 120 minutes.

[0071] This application provides the application of the composite flexible transparent electrode described in the above-described technical solutions or the composite flexible transparent electrode prepared by the preparation method described in the above-described technical solutions in flexible electronic devices. As one embodiment of this application, the flexible electronic device may include a flexible optoelectronic device, a flexible sensor, or a flexible display; the flexible optoelectronic device may include a flexible photovoltaic device, a flexible organic light-emitting semiconductor (OLED), a flexible photon receiver, or a flexible optical communication device; the flexible photovoltaic device may include a flexible perovskite solar cell, a flexible silicon thin-film solar cell, a flexible silicon-perovskite solar cell, a flexible copper indium gallium selenide thin-film solar cell, a flexible cadmium telluride solar cell, or a flexible organic solar cell.

[0072] The technical solutions of this application will be clearly and completely described below with reference to the embodiments therein. Obviously, the described embodiments are only a part of the embodiments of this application, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this application without creative effort are within the scope of protection of this application.

[0073] The transparent acrylic resin used in the following examples was prepared according to the method of Example 1 in Chinese Patent Application No. 202410666891.8; the release paper used was ultra-low roughness release paper (Ra = 10-40nm); and the molds used were ultra-smooth and ultra-clean molds.

[0074] Example 1

[0075] By weight, 100 parts of translucent acrylic resin, 10 parts of toughening agent (specifically LDPE 500026), 1 part of internal release agent (specifically LubeKote 6802) and 5 parts of nanofiller (specifically fumed silica) were internally extruded and mixed in a twin-screw internal extruder, then pulverized, passed through a 1000-mesh sieve, and the sieve-underfill material was collected to obtain a mixed powder;

[0076] The first release paper is laid in the lower mold, and the low-dielectric fiber fabric (specifically, low-dielectric cross-woven fiberglass cloth with a basis weight of 20 g / m²) is then placed inside. 2A 50×50cm, flat and wrinkle-free mixture (model HL2116) is laid on the surface of the first release paper. 50g of the mixed powder is spread on the surface of the translucent fiber fabric. A second release paper is laid on the mixed powder surface and covered with a mold. The entire assembly is then transferred to a laminator. The laminator pressure is increased to 1MPa and held for 5 minutes, then the pressure is reduced. This process is repeated three times to remove gas. The laminator pressure is then maintained at 0.1MPa. A heating program is set: the temperature is increased from room temperature to 40℃ at a rate of 5℃ / min and held for 10 minutes, then increased again at 5℃ / min. The temperature was increased from 40°C to 70°C and held for 5 minutes. Then, the temperature was increased from 70°C to 110°C at a rate of 5°C / min and held for 10 minutes. After that, the temperature was increased from 110°C to 150°C at a rate of 5°C / min and held for 45 minutes. The pressure was maintained at 0.1 MPa throughout the entire temperature program. After the above temperature program was completed, the temperature was reduced from 150°C to room temperature (25°C) at a rate of 10°C / min. The pressure was maintained at 1 MPa for 10 minutes during the cooling process. Finally, the mold was removed to obtain a fiberglass cloth reinforced resin high-transmittance substrate.

[0077] The fiberglass cloth reinforced resin high-transmittance substrate is placed on a heating plate, and the heating plate temperature is set to 70°C. Liquid paraffin is placed in the center of the fiberglass cloth reinforced resin high-transmittance substrate. After the liquid paraffin is completely melted and spread, the liquid paraffin is evenly coated with a coating stick to form a liquid paraffin layer with a thickness of no more than 1μm. The fiberglass cloth reinforced resin high-transmittance substrate covered with the liquid paraffin layer is placed in a high-cleanliness mold (same as the lamination film mold) of a lamination equipment. The pressure is set to 0.1MPa and maintained for 3 hours to remove gas and excess liquid paraffin while achieving heat treatment strengthening. After that, heating is stopped, and after cooling to room temperature, the mold is removed to obtain a smoothed fiberglass cloth reinforced resin high-transmittance substrate.

[0078] The surface of the smoothed fiberglass cloth reinforced resin high-transmittance substrate was wiped with anhydrous ethanol and then purged with high-purity nitrogen. The magnetron sample chamber of the magnetron sputtering equipment was opened, the smoothed fiberglass cloth reinforced resin high-transmittance substrate was placed on the sample stage, and an indium tin oxide target (In2O3 to SnO2 molar ratio of 9:1) was installed at the DC source target position. The target-substrate distance was adjusted to 7 cm, and the vacuum was evacuated to 1 × 10⁻⁶. -4 The sputtering program was set as follows: sputtering current 0.5 A, sputtering voltage 300 V, substrate bias 0 V, sputtering power 200 W, sputtering gas pressure (argon, 99.99% purity) 0.5 Pa, argon (99.99% purity) flow rate 10 sccm, substrate temperature 110 °C, and sputtering time 60 s. The sputtering program was started, and after completion, the vacuum was released, and the resulting sample film was placed in the annealing sample chamber of the magnetron sputtering equipment. The vacuum was then evacuated to 1 × 10⁻⁶ Pa.-3 After stabilizing at 200°C for 2 minutes, the substrate is annealed at 200°C for 5 minutes to form an ITO conductive coating with a thickness of 100 nm on the surface of the smoothed glass fiber cloth reinforced resin high-transmittance substrate, thus obtaining a composite flexible transparent electrode.

[0079] Example 2

[0080] A planarized glass fiber cloth reinforced resin high-transmittance substrate was prepared according to the method in Example 1;

[0081] Silver nanowires (5–300 μm in length and 20–200 nm in diameter) were dispersed in an alcohol solvent (specifically isopropanol) to obtain a silver nanowire dispersion (concentration 5 mg / mL). The silver nanowire dispersion was dropped onto the surface of a planarized glass fiber reinforced resin high-transmittance substrate and spin-coated at a low speed of 600 rpm for 1 min, followed by spin-coating at a high speed of 3000 rpm for 0.5 min. The low-speed spin-coating and high-speed spin-coating were repeated sequentially. The substrate was then dried at 140 °C for 2 h and pressed under a pressure of 10 MPa for 30 s to form a 500 nm thick conductive coating of silver nanowires on the surface of the planarized glass fiber reinforced resin high-transmittance substrate, thus obtaining a composite flexible transparent electrode.

[0082] Example 3

[0083] A planarized glass fiber cloth reinforced resin high-transmittance substrate was prepared according to the method in Example 1;

[0084] Carbon nanotubes (diameter 2-100 nm, length in the micrometer range), sodium dodecyl sulfate, water, and an alcohol solvent (specifically ethanol) were mixed to obtain a carbon nanotube dispersion (carbon nanotube concentration 0.5 wt%, sodium dodecyl sulfate concentration 5 wt%, water to alcohol solvent volume ratio 1:1). The carbon nanotube dispersion was loaded into a spray gun, and the distance between the spray gun nozzle and the smoothed fiberglass cloth reinforced resin high-transmittance substrate was set to 15 cm. The spray gun was turned on to uniformly spray the carbon nanotube dispersion onto one side of the smoothed fiberglass cloth reinforced resin high-transmittance substrate. After drying at 60 °C for 6 h, the substrate was rinsed with 50% nitric acid to remove sodium dodecyl sulfate. Finally, the substrate was heat-treated at 50 °C for 1 h to form a 500 nm thick carbon nanotube conductive coating on the surface of the smoothed fiberglass cloth reinforced resin high-transmittance substrate, thus obtaining a composite flexible transparent electrode.

[0085] Comparative Example 1

[0086] The composite flexible transparent electrode was prepared according to the method of Example 1, except that the planarized glass fiber cloth reinforced resin high light transmittance substrate was replaced with a commercial PET substrate.

[0087] Test Example 1

[0088] The performance of the smoothed glass fiber cloth reinforced resin high-transmittance substrate prepared in Example 1 and the commercial PET substrate in Comparative Example 1 were tested, and the results are shown in Table 1. As can be seen from Table 1:

[0089] 1. The light transmittance of the smoothed glass fiber cloth reinforced resin high-transmittance substrate in this application is 7.8% higher than that of commercial PET substrate, and the ultraviolet light transmittance is only 18%, which is far lower than the 83% of commercial PET;

[0090] 2. The roughness of the smoothed glass fiber cloth reinforced resin high-transmittance substrate in this application is at the same level as that of commercial PET substrates;

[0091] 3. In this application, the water vapor transmission rate and oxygen transmission rate of the smoothed glass fiber cloth reinforced resin high-transmittance substrate are both lower than those of commercial PET substrates;

[0092] 4. The mechanical properties and thermal stability (including tensile strength, glass transition temperature, thermal shrinkage rate, and curling) of the planarized glass fiber cloth reinforced resin high-transmittance substrate in this application are superior to those of commercial PET substrates.

[0093] 5. The smoothed fiberglass cloth reinforced resin high-transmittance substrate in this application has better weather resistance.

[0094] Table 1. Performance indicators of the smoothed fiberglass cloth reinforced resin high-transmittance substrate and commercial PET substrate in Example 1

[0095] Test Example 2

[0096] The performance of the composite flexible transparent electrodes prepared in Examples 1-3 and Comparative Example 1 was tested, and the results are shown in Table 2. As can be seen from Table 2, the composite flexible transparent electrodes prepared in this application using indium tin oxide, silver nanowires, and carbon nanotube conductive coatings on a fiber-reinforced resin high-transmittance substrate all exhibit optical, electrical, and mechanical properties that meet the usage standards. Furthermore, compared to composite flexible transparent electrodes using commercial PET as a substrate with the same conductive coating, the composite flexible transparent electrodes prepared in this application using the aforementioned fiber-reinforced resin high-transmittance substrate demonstrate superior optical, electrical, and mechanical properties, showing excellent application prospects in flexible optoelectronic devices such as flexible photovoltaic devices.

[0097] Table 2 Performance indicators of composite flexible transparent electrodes in Examples 1-3 and Comparative Example 1

[0098] The above description is only a preferred embodiment of this application. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of this application, and these improvements and modifications should also be considered within the scope of protection of this application.

Claims

1. A composite flexible transparent electrode, comprising a fiber fabric reinforced resin high-transmittance substrate and a conductive coating stacked together, wherein the fiber fabric reinforced resin high-transmittance substrate comprises a light-transmitting resin matrix and light-transmitting fiber fabric distributed in the light-transmitting resin matrix.

2. The composite flexible transparent electrode according to claim 1, characterized in that, The thickness of the fiber-reinforced resin high-transmittance substrate is 100–300 μm; the thickness of the conductive coating is 20–1000 nm.

3. The composite flexible transparent electrode according to claim 1, characterized in that, The raw materials for preparing the translucent resin matrix, by mass fraction, include 100 parts of translucent acrylic resin, 0.1 to 10 parts of toughening agent, and 0.3 to 10 parts of nanofiller; the mass ratio of the translucent resin matrix to the translucent fiber fabric is 1 to 10:

1.

4. The composite flexible transparent electrode according to claim 3, characterized in that, The toughening agent includes low-density polyethylene powder, MOUSSEX S 667, MOUSSEX SF 561, or... COC 6013F-4.

5. The composite flexible transparent electrode according to claim 4, characterized in that, The low-density polyethylene powder includes LDPE 500026 or LDPE 200024.

6. The composite flexible transparent electrode according to claim 3, characterized in that, The nanofiller includes one or more of fumed silica, fumed alumina, nanocellulose, and nanobarium oxide.

7. The composite flexible transparent electrode according to claim 3, characterized in that, The raw materials for preparing the translucent resin matrix also include 0.1 to 5 parts of internal release agent.

8. The composite flexible transparent electrode according to claim 7, characterized in that, The internal release agent is LubeKote 6802.

9. The composite flexible transparent electrode according to claim 1, characterized in that, The fibers in the translucent fiber fabric include one or more of glass fibers, carbon fibers, and basalt fibers; the basis weight of the translucent fiber fabric is 20–100 g / m². 2 .

10. The composite flexible transparent electrode according to claim 1, characterized in that, Under light wavelengths of 400–1100 nm, the transmittance of the fiber-reinforced resin high-transmittance substrate is 80–92.8%.

11. The composite flexible transparent electrode according to any one of claims 1 to 10, characterized in that, The method for preparing the fiber-reinforced resin high-transmittance substrate includes the following steps: The raw materials for preparing the translucent resin matrix are mixed to obtain a mixed powder; The mixed powder is spread on the surface of a light-transmitting fiber fabric and laminated to obtain the fiber fabric-reinforced resin high-transmittance substrate.

12. The composite flexible transparent electrode according to claim 11, characterized in that, The process before lamination also includes venting; the venting includes sequentially increasing, holding and decreasing the pressure, and the number of venting cycles is 1 to 5; the holding pressure during each venting is 0.5 to 3 MPa, and the holding time is 5 to 15 minutes; the venting is carried out at room temperature.

13. The composite flexible transparent electrode according to claim 11 or 12, characterized in that, The lamination pressure is 0.1 to 3 MPa; the lamination adopts a programmed temperature rise, which includes: raising the temperature from room temperature to a first holding temperature at a first heating rate and holding it for a first time, raising the temperature to a second holding temperature at a second heating rate and holding it for a second time, raising the temperature to a third holding temperature at a third heating rate and holding it for a third time, and then raising the temperature to a fourth holding temperature at a fourth heating rate and holding it for a fourth time. The first heating rate, the second heating rate, and the third heating rate are each independently 3–10 °C / min, and the fourth heating rate is 3–5 °C / min; the first holding temperature is 30–50 °C, and the first holding time is 5–20 min; the second holding temperature is 70–100 °C, and the second holding time is 1–10 min; the third holding temperature is 110–130 °C, and the third holding time is 5–20 min; the fourth holding temperature is 140–170 °C, and the fourth holding time is 15–60 min.

14. The composite flexible transparent electrode according to claim 11, characterized in that, The surface of the fiber-reinforced resin high-transmittance substrate that is in contact with the conductive coating is also distributed with a surface treatment agent. When the surface treatment agent is distributed on the fiber-reinforced resin high-transmittance substrate, the lamination process further includes: using the surface treatment agent to smooth the surface of the laminated composite film that is to be in contact with the conductive coating, thereby obtaining the fiber-reinforced resin high-transmittance substrate.

15. The composite flexible transparent electrode according to claim 14, characterized in that, The surface treatment agent includes liquid paraffin, polymethyl methacrylate, polydimethylsiloxane, or polyimide.

16. The composite flexible transparent electrode according to claim 14 or 15, characterized in that, The leveling process includes: coating the surface of the laminated composite film to be in contact with the conductive coating with a surface treatment agent, and then performing heat treatment to strengthen it.

17. The composite flexible transparent electrode according to claim 16, characterized in that, The thickness of the surface treatment agent coating formed by the surface treatment agent is 0.2 to 3 μm.

18. The composite flexible transparent electrode according to claim 16 or 17, characterized in that, The heat treatment strengthening temperature is 70–140°C, and the time is 1–24 h.

19. The composite flexible transparent electrode according to claim 1, characterized in that, The conductive material used in the conductive coating includes one or more of indium tin oxide, silver nanowires, and carbon nanomaterials.

20. The composite flexible transparent electrode according to claim 19, characterized in that, The composition of the indium tin oxide is based on the ratio of indium oxide to tin oxide, and the molar ratio of indium oxide to tin oxide is 9:

1.

21. The composite flexible transparent electrode according to claim 19, characterized in that, The silver nanowires have a length of 5–300 μm and a diameter of 20–200 nm.

22. The composite flexible transparent electrode according to claim 19, characterized in that, The carbon nanomaterials include graphene and / or carbon nanotubes; the thickness of the graphene sheets is 0.4–10 nm; and the diameter of the carbon nanotubes is 2–100 nm.

23. A method for preparing the composite flexible transparent electrode according to any one of claims 1 to 22, comprising the following steps: A conductive coating is prepared on one side of a fiber-reinforced resin high-transmittance substrate to obtain the composite flexible transparent electrode.

24. The preparation method according to claim 23, characterized in that, When the conductive material used in the conductive coating is indium tin oxide, the conductive coating is prepared by magnetron sputtering.

25. The preparation method according to claim 24, characterized in that, The magnetron sputtering method includes DC sputtering, medium-frequency magnetron sputtering, double-click magnetron sputtering, or plasma-enhanced magnetron sputtering.

26. The preparation method according to claim 24 or 25, characterized in that, The magnetron sputtering method includes sputtering and annealing in sequence; The sputtering conditions include: a target-to-substrate distance of 5–10 cm and a background vacuum of 2.0 × 10⁻⁶. -3 Below Pa, the sputtering current is 0.5–0.7 A, the sputtering voltage is 300–500 V, the substrate bias voltage is -200 V to 0 V, the sputtering power is 100–500 W, the sputtering gas pressure is 0.1–2.5 Pa, the argon flow rate is 10–20 sccm, the oxygen flow rate is 0–2 sccm, the substrate temperature is 110–170 °C, and the sputtering time is 30–60 s; The annealing conditions include: a temperature of 170–200°C and a holding time of 1–5 min; the annealing is carried out under vacuum conditions.

27. The preparation method according to claim 23, characterized in that, When the conductive material used in the conductive coating is silver nanowires, the preparation of the conductive coating is carried out using a wet process, which includes the following steps: Silver nanowires were dispersed in an alcohol solvent to obtain a silver nanowire dispersion; the silver nanowire dispersion was coated on one side of the fiber-reinforced resin high-transmittance substrate, dried, and then pressed to obtain the composite flexible transparent electrode.

28. The preparation method according to claim 27, characterized in that, The alcohol solvent includes ethanol and / or isopropanol, and the concentration of the silver nanowire dispersion is 4–20 mg / mL; the coating is spin coating, and each spin coating includes sequential low-speed spin coating and high-speed spin coating. The rotation speed of each low-speed spin coating is 500–3000 rpm, and the time is 10–120 s; the rotation speed of each high-speed spin coating is 3000–6000 rpm, and the time is 5–60 s; the pressing pressure is 5–25 MPa, and the holding time is 10–60 s.

29. The preparation method according to claim 23, characterized in that, When the conductive material used in the conductive coating is carbon nanomaterial, the method for preparing the conductive coating includes the following steps: mixing carbon nanomaterial, dispersant and solvent to obtain carbon nanomaterial dispersion; coating the carbon nanomaterial dispersion on one side of the fiber fabric reinforced resin high transmittance substrate, drying and washing to remove the dispersant, and then heat-treating to obtain the composite flexible transparent electrode.

30. The preparation method according to claim 29, characterized in that, The dispersant is sodium dodecyl sulfate, the solvent is water and / or alcohol, and the concentration of carbon nanomaterials in the carbon nanomaterial dispersion is 0.1-1.5 wt%. The coating is spraying. The heat treatment temperature is 30-70°C, and the holding time is 30-120 min.

31. The application of the composite flexible transparent electrode according to any one of claims 1 to 22 or the composite flexible transparent electrode prepared by the preparation method according to any one of claims 23 to 30 in flexible electronic devices.

32. The application according to claim 31, characterized in that, The flexible electronic device includes flexible optoelectronic devices, flexible sensors, or flexible displays; the flexible optoelectronic devices include flexible photovoltaic devices, flexible organic light-emitting semiconductors, flexible photon receivers, or flexible optical communication devices; the flexible photovoltaic devices include flexible perovskite solar cells, flexible silicon thin-film solar cells, flexible silicon-perovskite solar cells, flexible copper indium gallium selenide thin-film solar cells, flexible cadmium telluride solar cells, or flexible organic solar cells.

33. A flexible electronic device, comprising the composite flexible transparent electrode according to any one of claims 1 to 22 or the composite flexible transparent electrode prepared by the preparation method according to any one of claims 23 to 30.

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