ETFE cadmium telluride film photovoltaic power generation module with high-durability plating point and preparation method of ETFE cadmium telluride film photovoltaic power generation module

Abstract

The invention discloses a high-durability plating point ETFE cadmium telluride film photovoltaic power generation module and a preparation method thereof. The photovoltaic power generation module comprises an ETFE protection layer, an ETFE plating point sunshade layer, a transparent conductive oxide layer, a cadmium telluride solar cell layer, a back contact layer and a conductive electrode which are sequentially stacked from top to bottom, wherein the ETFE plating point sunshade layer comprises an ETFE thin film and plating points on the ETFE thin film. The ETFE thin film designed through the plating points not only plays a protection role, but also can realize the optimal management and sunshade effect of sunlight by accurately regulating and controlling the sizes, shapes and intervals of the plating points.

Description

Technical Field

[0001] The invention relates to the technical field of photoelectric conversion and solar energy utilization, and in particular to a high-durability plated ETFE (ethylene-tetrafluoroethylene) cadmium telluride thin film photovoltaic power generation module and a preparation method thereof. Background Art

[0002] With the growing global demand for sustainable clean energy and technological advancement, cadmium telluride thin-film solar cells have attracted widespread attention due to their cost-effectiveness, thin and light characteristics, and good weak light response performance. However, when traditional cadmium telluride thin-film solar cells operate for a long time under strong light conditions, their weather resistance is a key factor affecting their service life. In recent years, ETFE dot-plated films have been widely used in roof packaging materials for facilities such as large stadiums due to their excellent sun shading and outstanding weather resistance. However, the currently used dot-plating process materials are prone to plating shedding after 3 to 5 years of outdoor environment exposure, resulting in a significant decrease in the sun shading effect or even failure, which seriously affects the long-term stability and working efficiency of the photovoltaic system.

[0003] Chinese patent application CN201810665289.7 discloses an improved cadmium telluride thin-film solar cell and its preparation method. By adopting a back contact structure, the contact barrier with cadmium telluride is effectively reduced and ohmic contact is achieved. The double-layer back contact design further enhances the carrier conductivity and improves the overall performance of the battery. Although this technology has successfully alleviated the efficiency attenuation and production cost problems caused by copper doping diffusion in traditional cadmium telluride batteries, there are still the following technical bottlenecks in practical applications: Limited light transmittance: Since the back electrode layer is made of opaque material, this limits the applicability of the cadmium telluride thin-film solar cell in application scenarios such as building facades that have high light transmittance requirements. Lack of protection mechanism: The patent document does not mention a specific protective layer design, which makes cadmium telluride thin-film solar cells susceptible to moisture, oxygen, ultraviolet radiation and other factors in the complex outdoor natural environment, resulting in a relatively short battery life. Insufficient thermal insulation performance: Under direct sunlight, the battery structure is not equipped with effective thermal insulation measures, which may cause the battery temperature to rise rapidly. High temperature will directly affect the battery's photoelectric conversion efficiency, resulting in a decrease in power generation performance.

[0004] In summary, the existing technology still has problems such as insufficient protection of key components, poor weather resistance under strong light, and poor light transmittance of photovoltaic systems. Summary of the invention

[0005] The purpose of the present invention is to provide a high-durability ETFE (ethylene-tetrafluoroethylene) cadmium telluride thin film photovoltaic power generation module and a preparation method thereof.

[0006] The present invention is achieved through the following technical scheme: a high-durability ETFE (ethylene-tetrafluoroethylene) cadmium telluride thin film photovoltaic power generation module, comprising an ETFE protective layer, an ETFE plated sunshade layer, a transparent conductive oxide layer, a cadmium telluride solar cell layer, a back contact layer and a conductive electrode stacked in sequence from top to bottom, wherein the ETFE plated sunshade layer comprises an ETFE film and plated dots on the ETFE film.

[0007] The photovoltaic power generation module also includes a supporting frame for placement and fixation.

[0008] Furthermore, the transparent conductive electrode is prepared by combining a graphene film with an aluminum-doped zinc oxide (AZO) film.

[0009] Furthermore, the transparent conductive oxide layer is a composite oxide of silicon dioxide (SiO2) and ion-doped cerium oxide (CeO2).

[0010] Furthermore, the cadmium telluride solar cell layer includes a cadmium sulfide (CdS) window layer and a cadmium telluride (CdTe) absorption layer.

[0011] The present invention also provides a photovoltaic power generation system, comprising a photovoltaic power generation module, an inverter control module and an energy storage module, wherein the inverter control module is connected to the photovoltaic power generation module and the energy storage module respectively.

[0012] On the other hand, the present invention provides a method for preparing a high-durability plated ETFE cadmium telluride thin film photovoltaic power generation module, the steps of which are as follows:

[0013] Step 1: Paste a layer of ETFE protective layer on the front of the support frame;

[0014] Step 2: Plating dots on the ETFE film to obtain an ETFE plating dot sunshade layer, and the ETFE plating dot sunshade layer is tightly connected with the top ETFE protective layer by high temperature hot pressing;

[0015] Step 3: Make a transparent conductive oxide layer under the ETFE plated sunshade layer;

[0016] Step 4: Using the transparent conductive oxide layer as a substrate, a cadmium telluride solar cell layer is fabricated;

[0017] Step 5: Fabricate a back contact layer below the cadmium telluride solar cell layer;

[0018] Step 6: Making Conductive Electrodes.

[0019] Further preferably, step 2 is specifically as follows: by plating dots on the ETFE film, for building walls facing east and west, designing asymmetric elliptical plating dots with a major axis range of 10-20 mm and a minor axis range of 5-15 mm, using a pattern mask with a grid spacing of 20-1000 microns in the plating dot spacing range; for building walls facing north or south, using a circular plating dot design with a diameter range of 5-15 mm, using a pattern mask with a grid spacing of 50-2000 microns in the plating dot spacing range.

[0020] Further preferably, the preparation method of the transparent conductive oxide layer is as follows:

[0021] (1) First, a precursor solution is prepared according to a ratio of cerium nitrate (Ce(NO3)3) and aluminum nitrate (Al(NO3)3) in molar concentrations of 0.4-0.6 M; an appropriate amount of diluted ammonia water is added to the precursor solution, and the pH value is adjusted to 5.0-6.0 to obtain a sol;

[0022] (2) The prepared sol is uniformly coated on a glass substrate pre-coated with an ITO film by spin coating technology to form a preliminary dry gel film;

[0023] (3) placing the substrate with the dry gel film in a program-controlled furnace, gradually raising the temperature to 500°C at a heating rate of 10-30°C / h in air, and maintaining this temperature for 4-5 hours for constant temperature treatment, after which the substrate is allowed to cool naturally to room temperature in the furnace;

[0024] (4) Using a surface profiler to accurately measure and control the film thickness, a silicon dioxide-doped cerium oxide composite oxide with a thickness of 30-40 nanometers is finally formed as a transparent conductive oxide layer.

[0025] Further preferably, in step 4, the transparent conductive oxide layer is used as a substrate, and a physical vapor deposition technique is used to deposit an n-type cadmium sulfide layer on the transparent conductive oxide layer substrate; and a p-type cadmium telluride thin film is deposited on the n-type cadmium sulfide layer by electrochemical deposition to obtain a cadmium telluride solar cell layer.

[0026] Further preferably, in step 5, a back contact layer is formed below the cadmium telluride solar cell layer by depositing metal molybdenum.

[0027] Further preferably, the process of making the transparent conductive electrode is as follows:

[0028] The copper foil is used as the anode and the cathode material is used as the cathode, which are placed in an electrolyte for electropolishing treatment, and the electropolished copper foil is placed in an oven for drying.

[0029] Using a fully automatic graphene transfer system, graphene was transferred from the copper foil to the target substrate for copper corrosion. Magnetron sputtering technology was used to sputter-deposit aluminum-doped zinc oxide (AZO, ZnO:Al2O3 mass ratio 97:3) and indium tin oxide (ITO, In2O3:SnO2 mass ratio 85:15 to 95:5) as transparent conductive oxide thin film materials, and finally a transparent conductive electrode was formed.

[0030] The working principle of the present invention is as follows: Sunlight first passes through the ETFE-plated sunshade layer, which can not only transmit an appropriate amount of sunlight for absorption by the cadmium telluride solar cell, but also effectively suppress the overheating of the battery caused by excessive light, thereby maintaining the battery at a suitable operating temperature. Sunlight passes through the TCO layer to irradiate the cadmium telluride solar cell layer, and the electrons in the cadmium telluride material are excited to transition, generating electron-hole pairs, thereby forming current. The current passes through the back contact layer and the transparent conductive electrode in turn, and is converted into alternating current under the action of the inverter control module. The energy storage module stores and releases electricity in a timely manner to ensure continuous and reliable power supply.

[0031] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: (1) The high-durability plated ETFE film used has excellent weather resistance, can operate stably for a long time in outdoor environments, resist the effects of ultraviolet rays, wind and rain erosion and temperature changes, and significantly extend the service life of cadmium telluride thin film solar cells; (2) The plated ETFE film not only plays a protective role, but also can achieve optimized management and shading effect of sunlight by precisely controlling the size, shape and spacing of the plated spots, reduce the loss of battery efficiency caused by overheating, and maintain sufficient light transmittance for solar cells to efficiently absorb light energy; for different incident angles, a shape-optimized mask or template is used, and photolithography technology or precision template printing technology is used to make the plated spots into specific geometric shapes (such as ellipse, diamond, etc.) to maximize the use of sunlight at different angles. For light with a larger incident angle, an asymmetric plated spot shape can be designed to improve the light refraction efficiency and reduce reflection loss. Regulation of the spacing between the plated spots: A pattern mask with different grid spacings is used to control the spacing between the plated spots. For vertically incident sunlight at noon, a larger spacing between plating points can be used to ensure light penetration; for oblique incident light in the early morning or evening, the spacing between plating points should be reduced accordingly to enhance the shading effect and reduce heat accumulation. The spacing between plating points can be adjusted between 1 micron and 200 microns. Through the above steps, the plating point design of the present invention not only effectively protects the film, but also can reduce the loss of battery efficiency caused by overheating while ensuring efficient light energy absorption by solar cells, thereby achieving the effect of optimizing the management of sunlight. (3) The ETFE film itself has the characteristics of light weight and flexibility, making the photovoltaic system easier to install and adapt to different curved surfaces or special structures, expanding its application range in construction and other fields; (4) For transparent electrodes, appropriate graphene doping can optimize the resistivity and significantly improve its conductive properties while retaining good optical properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 This is a schematic diagram of the structure of the high-durability photovoltaic power generation thin film module of the present invention;

[0033] Figure 2 is a schematic diagram of a photovoltaic power generation system of the present invention;

[0034] Figure 3 This is a design diagram of the plating points and the position of the cadmium telluride solar cell of the present invention.

[0035] In the figure, 1. aluminum alloy frame; 2. ETFE protective layer; 3. ETFE plated sunshade layer; 31. plated; 32. ETFE film; 4. transparent conductive oxide layer; 5. cadmium telluride solar cell layer; 6. back contact layer; 7. transparent conductive electrode; 8. photovoltaic inverter control integrated machine; 9. energy storage battery; 10. wire. DETAILED DESCRIPTION

[0036] The technical solution of the present invention is further described below in conjunction with the accompanying drawings.

[0037] Example 1

[0038] like Figure 1 A high-durability plated ETFE cadmium telluride thin film photovoltaic power generation module comprises an ETFE protective layer 2, an ETFE plated sunshade layer 3, a transparent conductive oxide layer 4, a cadmium telluride solar cell layer 5, a back contact layer 6 and a transparent conductive electrode 7 which are stacked in sequence from top to bottom. The ETFE protective layer 2, the ETFE plated sunshade layer 3, the transparent conductive oxide layer 4, the cadmium telluride solar cell layer 5, the back contact layer 6 and the transparent conductive electrode 7 are fixedly supported by an aluminum alloy frame 1 to constitute a high-durability photovoltaic power generation thin film module. The ETFE plated sunshade layer 3 comprises an ETFE film 32 and plated dots 31 on the ETFE film 32.

[0039] A method for preparing a high-durability plated ETFE cadmium telluride thin film photovoltaic power generation module, the steps are as follows:

[0040] Step 1: The aluminum alloy frame 1 serves as the mechanical support structure of the entire thin film device to ensure the stability and durability of the device. A layer of ETFE protective layer 2 is pasted on the front, which is tightly bonded through the 10mm prefabricated grooves of the aluminum alloy frame 1, and then the grooves are sealed with epoxy resin. The thickness of the ETFE protective layer 2 is 200 microns, providing excellent weather resistance, chemical stability and light transmittance to protect the internal structure from environmental damage.

[0041] Step 2: Then, by plating dots on the ETFE film 32, for the building wall facing east and west, considering the oblique sunlight in the early morning and evening, an asymmetric elliptical plating dot is designed with a major axis of 15 mm and a minor axis of 10 mm to improve the light refraction efficiency and reduce reflection loss, and a pattern mask with a grid spacing of 500 microns is used to enhance the sunshade effect and reduce heat accumulation. For the building wall facing north or south, for the sunlight incident vertically at noon, a circular plating dot design with a diameter of 10 mm is used to ensure the effective use of light, and a pattern mask with a grid spacing of 1000 microns is used to ensure the light is transmitted. In order to reserve space for direct light exposure to the cadmium telluride solar cell layer 5, an ETFE plating dot sunshade layer 3 with sunshade function is prepared. The ETFE plated sunshade layer 33 has a thickness of 250 microns and is tightly connected to the top ETFE protective layer 1 through high-temperature hot pressing, thereby ensuring light transmission and sunshade effects without damaging the transparent conductive oxide layer 4 underneath.

[0042] Step 3: Install the transparent conductive oxide layer 4 under the ETFE plated sunshade layer 3.

[0043] The preparation method of the transparent conductive oxide layer is as follows:

[0044] (1) First, a precursor solution is prepared according to a molar concentration ratio of cerium nitrate (Ce(NO3)3) and aluminum nitrate (Al(NO3)3) of 0.5 M. An appropriate amount of diluted ammonia water is added to the solution, and the pH value is adjusted to 5.5 to ensure that the solution is stable.

[0045] (2) The prepared sol was uniformly coated on a glass substrate pre-coated with an ITO film by spin coating technology, with the coating speed set at 450 rpm and the coating time set at 10 seconds to form a preliminary dry gel film.

[0046] (3) The substrate with the dry gel film was placed in a program-controlled furnace, and the temperature was gradually raised to 500°C at a heating rate of 20°C / h in air, and maintained at this temperature for 4.5 hours for constant temperature treatment. After that, the substrate was allowed to cool naturally to room temperature in the furnace.

[0047] (4) The film thickness is precisely measured and controlled using a surface profiler, and finally a silicon dioxide-doped cerium oxide composite oxide with a thickness of 35 nanometers is formed as the transparent conductive oxide layer 4.

[0048] Step 4: Using the transparent conductive oxide layer 4 as a substrate, a uniform n-type cadmium sulfide layer with a thickness of 400 nanometers is deposited on the transparent conductive oxide layer 4 substrate using physical vapor deposition technology. This cadmium sulfide layer has a small bandgap width, which can effectively guide sunlight to enter and prevent electron-hole pairs from recombining at the interface; a p-type cadmium telluride film with a thickness of 2 microns is deposited on the n-type cadmium sulfide layer by electrochemical deposition to fully absorb sunlight, thereby obtaining a cadmium telluride solar cell layer 5.

[0049] Step 5: Under the cadmium telluride solar cell layer 5, a back contact layer 6 is formed by depositing metal molybdenum (Mo) to ensure that an efficient electron collection network is formed between it and the cadmium telluride solar cell layer 5, and at the same time, a good contact is formed with the transparent conductive electrode 7 to be deposited in the next step.

[0050] Step 6: Making a transparent conductive electrode.

[0051] Select a copper foil with a purity of ≥99.9% and a thickness of 55 microns, and use scissors to cut the copper foil into standard rectangular pieces of 5cm×6cm. Prepare a container and add enough 60wt% phosphoric acid solution to ensure that the copper foil is completely immersed. Place the cut copper foil in the phosphoric acid solution and soak for 5 minutes. After soaking, use tweezers to carefully remove the copper foil and rinse it with deionized water to remove residual phosphoric acid. Prepare an electropolishing device, including an electrolyte (a mixture of sulfuric acid and chromic acid), a power supply, and a cathode material (such as stainless steel). Place the copper foil as the anode and the cathode material as the cathode in the electrolyte. Set the current density to 1A / cm 2 Perform electropolishing for 10 minutes. After completion, wash the copper foil with deionized water to remove electrolyte residue. Place the electropolished copper foil in an oven, heat the container to 80°C, and maintain this temperature for 10 minutes. After the treatment is completed, turn off the heating source and let the copper foil cool naturally to room temperature.

[0052] In a four-inch cold-wall CVD reactor, the Ar, H2, and CH4 gas environments were first purified, and then a mixed gas of 1% CH4, 32% H2, and 67% Ar was injected into the argon environment at 1000°C, maintaining a pressure of 60 mbar, and growing a graphene monolayer film for 20 minutes. Using a fully automatic graphene transfer system, the graphene was transferred from the copper foil to the target substrate through full fluid manipulation technology without mechanical damage and contamination. Copper was etched using 0.4M ammonium persulfate, and the transfer was finally completed using deionized water. Using magnetron sputtering technology, the basic vacuum degree was 1×10 -5 In the Pa system, 99.999% pure argon was used as the sputtering gas, and RF and DC power supplies were used to sputter and deposit aluminum-doped zinc oxide (AZO, ZnO:Al2O3 mass ratio 97:3) and indium tin oxide (ITO, In2O3:SnO2 mass ratio 89:11) as transparent conductive oxide thin film materials, and finally a transparent conductive electrode with a thickness of 150 nanometers was formed7.

[0053] Example 2

[0054] like Figure 2As shown, a photovoltaic power generation system includes the photovoltaic power generation module, the inverter control module and the energy storage module described in Example 1, wherein the inverter control module is connected to the photovoltaic power generation module and the energy storage module respectively through a wire 10, the inverter control module is a photovoltaic inverter control integrated machine 8, and the energy storage module is an energy storage battery 9; the direct current generated by the photovoltaic power generation module must first be transmitted to the photovoltaic inverter control integrated machine 8 through the wire 10, ensuring that the positive pole (+) of the photovoltaic power generation module is connected to the input positive terminal of the photovoltaic inverter control integrated machine 8, and the negative pole (-) is connected to the input negative terminal of the photovoltaic inverter control integrated machine 8. The positive pole of the energy storage battery 9 is connected to the positive charging port of the photovoltaic inverter control integrated machine 8, and the negative pole is connected to the negative charging port of the photovoltaic inverter control integrated machine 8. The photovoltaic inverter control integrated machine 8 will automatically monitor and control the charging and discharging process of the energy storage battery 9 to protect the energy storage battery 9 from being overcharged or over-discharged.

[0055] like Figure 3 As shown, in the design of cadmium telluride thin film solar cells, in order to maximize the area of ​​the cell to receive sunlight, a strategy is adopted to avoid setting shielding plating points in the main area of ​​the cell. The ETFE film with silver-gray sunscreen plating points can reflect part of the solar radiation and reduce the temperature rise inside the component without affecting the light transmittance. During the design, the plating points should be located in the interval area between the cadmium telluride solar cell units. Such a layout can ensure that the sunlight directly hits the surface of the cadmium telluride thin film cell, and can provide the necessary electrode connection and shading effect without affecting the front light of the cell. This design can not only improve the overall efficiency of the cell, but also improve the operating temperature of the component, thereby indirectly improving the long-term stability and service life of the solar cell. The overall size of the photovoltaic power generation module is 260 mm long and 260 mm wide. Each cadmium telluride thin film area is a 46 mm square with an interval of 10 mm. No plating points are set directly above each cadmium telluride thin film area to ensure that the active area of ​​the cadmium telluride solar cell layer 5 is not blocked from receiving sunlight. Each plating point has a diameter of 10 mm and a spacing of 2 mm between the plating points. While being able to reflect a portion of the incident solar radiation and reduce the operating temperature of the module, it hardly affects the transmission of sunlight to the active area of ​​the cadmium telluride solar cell layer 5. The distance between the cadmium telluride solar cell layer 5 and the aluminum alloy frame is set to 15 mm for wiring. In this embodiment, the total front area of ​​the photovoltaic power generation module is 67600 mm 2 The total CdTe film area is 33856mm 2 The total plating area is 8242.5mm 2 .

[0056] The materials prepared in Example 1 were assembled in the manner of Example 2, and the power generation of the system and the peak temperature of the cadmium telluride thin film solar cell in one day in summer were recorded under different arrangements of the plating points.

[0057] Table 1 Power generation and peak temperature under different plating point arrangements

[0058]

[0059] The power generation is the highest when there is no plating, but the peak temperature is as high as 68.4℃, which may be detrimental to the long-term stability and life of the battery. The peak temperature of the circular plating point 10mm is the lowest, but the power generation is also the lowest. The power generation of the elliptical plating point 15x10 mm is reduced, but it is better than the circular plating point 10mm. This is because the short axis direction of the plating point helps the light absorption efficiency under the solar incident angle in the morning and evening. The power generation and peak temperature of the circular plating point 5mm and the elliptical plating point 10x5 mm are both ideal, especially the elliptical plating point 10x5 mm, whose power generation is close to the case of no plating point, and the peak temperature is better controlled.

[0060] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A high-durability ETFE cadmium telluride thin film photovoltaic power generation module, characterized in that: It comprises an ETFE protective layer, an ETFE dot-plated sunshade layer, a transparent conductive oxide layer, a cadmium telluride solar cell layer, a back contact layer and a conductive electrode which are stacked in sequence from top to bottom. The ETFE dot-plated sunshade layer comprises an ETFE film and dot-plated spots on the ETFE film.

2. The high-durability plated ETFE cadmium telluride thin film photovoltaic power generation module according to claim 1, characterized in that: The photovoltaic power generation module also includes a supporting frame for placement and fixation.

3. The high-durability plated ETFE cadmium telluride thin film photovoltaic power generation module according to claim 1, characterized in that: The transparent conductive electrode is prepared by combining a graphene film with an aluminum-doped zinc oxide film.

4. The high-durability plated ETFE cadmium telluride thin film photovoltaic power generation module according to claim 1, characterized in that: The transparent conductive oxide layer is a composite oxide of silicon dioxide and ion-doped cerium oxide.

5. The high-durability plated ETFE cadmium telluride thin film photovoltaic power generation module according to claim 1, characterized in that: The cadmium telluride solar cell layers include a cadmium sulfide (CdS) window layer and a cadmium telluride (CdTe) absorber layer.

6. A method for preparing a high-durability plated ETFE cadmium telluride thin film photovoltaic power generation module according to any one of claims 1 to 5, characterized in that: Here are the steps: Step 1: Paste a layer of ETFE protective layer on the front of the support frame; Step 2: Plating dots on the ETFE film to obtain an ETFE plating dot sunshade layer, and the ETFE plating dot sunshade layer is tightly connected with the top ETFE protective layer by high temperature hot pressing; Step 3: Make a transparent conductive oxide layer under the ETFE plated sunshade layer; Step 4: Using the transparent conductive oxide layer as a substrate, a cadmium telluride solar cell layer is fabricated; Step 5: Fabricate a back contact layer below the cadmium telluride solar cell layer; Step 6: Making Conductive Electrodes.

7. The method for preparing the high-durability plated ETFE cadmium telluride thin film photovoltaic power generation module according to claim 6, characterized in that: Step 2 is specifically as follows: by plating dots on the ETFE film, for building walls facing east and west, design asymmetric elliptical plating dots with a major axis range of 10-20 mm and a minor axis range of 5-15 mm, and use a pattern mask with a grid spacing of 20-100 microns for the plating dot spacing; for building walls facing north or south, use a circular plating dot design with a diameter range of 5-15 mm, and use a pattern mask with a grid spacing of 50-200 microns for the plating dot spacing.

8. The method for preparing the high-durability plated ETFE cadmium telluride thin film photovoltaic power generation module according to claim 6, characterized in that: The preparation method of the transparent conductive oxide layer is as follows: (1) First, a precursor solution is prepared according to a ratio of cerium nitrate (Ce(NO3)3) and aluminum nitrate (Al(NO3)3) in molar concentrations of 0.4-0.6 M; an appropriate amount of diluted ammonia water is added to the precursor solution, and the pH value is adjusted to 5.0-6.0 to obtain a sol; (2) The prepared sol is uniformly coated on a glass substrate pre-coated with an ITO film by spin coating technology to form a preliminary dry gel film; (3) placing the substrate with the dry gel film in a program-controlled furnace, gradually raising the temperature to 500°C at a heating rate of 10-30°C / h in air, and maintaining this temperature for 4-5 hours for constant temperature treatment, after which the substrate is allowed to cool naturally to room temperature in the furnace; (4) Using a surface profiler to accurately measure and control the film thickness, a silicon dioxide-doped cerium oxide composite oxide with a thickness ranging from 30 to 40 nanometers is finally formed as a transparent conductive oxide layer.

9. The method for preparing the high-durability plated ETFE cadmium telluride thin film photovoltaic power generation module according to claim 6, characterized in that: The process of making a transparent conductive electrode is as follows: The copper foil is used as the anode and the cathode material is used as the cathode, which are placed in an electrolyte for electropolishing treatment, and the electropolished copper foil is placed in an oven for drying. Using a fully automatic graphene transfer system, graphene is transferred from copper foil to the target substrate for copper corrosion. Magnetron sputtering technology is used to sputter and deposit aluminum-doped zinc oxide and indium tin oxide as transparent conductive oxide thin film materials, respectively, to finally form a transparent conductive electrode.

10. A photovoltaic power generation system, characterized in that: It comprises the photovoltaic power generation module, inverter control module and energy storage module as described in any one of claims 1 to 5, wherein the inverter control module is connected to the photovoltaic power generation module and the energy storage module respectively.

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