Flexible perovskite photovoltaic building material and preparation method thereof

Abstract

The application provides a flexible perovskite photovoltaic building material and a preparation method thereof, and the photovoltaic building material comprises a building material substrate and a flexible perovskite photovoltaic component which is bonded to the surface of the building material substrate, the flexible perovskite photovoltaic component comprises a perovskite photovoltaic cell, a front plate glass and a composite film layer which is arranged on the surface of the front plate glass facing the perovskite photovoltaic cell, the composite film layer is bonded to the perovskite photovoltaic cell, and the composite film layer comprises a graphene-aluminum oxide composite film layer, a transparent conductive oxide film layer and a silicon nitride layer which are sequentially deposited on the surface of the front plate glass facing the cell. According to the application, the three-layer composite film layer structure of the graphene-aluminum oxide composite film layer, the transparent conductive oxide film layer and the silicon nitride layer is constructed on the side of the front plate glass facing the cell, and an integrated 'heat dissipation-conduction-barrier' function integrated unit is formed.

Description

Technical Field

[0001] This invention relates to the field of photovoltaic building materials technology, and in particular to a flexible perovskite photovoltaic building material and its preparation method. Background Technology

[0002] Building Integrated Photovoltaics (BIPV) integrates solar energy systems into buildings, enabling them to function as buildings while utilizing energy generated on building surfaces, thus providing clean energy and reducing building energy consumption. Perovskite solar cells, which use perovskite-type organometal halide semiconductors as light-absorbing materials, possess excellent characteristics such as tunable bandgap, high absorption coefficient, and long carrier diffusion length, making them highly promising for BIPV applications.

[0003] However, perovskite solar cells still face several key technical bottlenecks in practical BIPV applications. First, perovskite materials are extremely sensitive to water vapor and oxygen; they decompose rapidly upon contact with water and fail after months of exposure to air, thus placing extremely high demands on encapsulation barrier performance. Second, the performance of perovskite solar cells is significantly affected by temperature; increased temperature accelerates ion migration and phase transition decomposition, leading to irreversible efficiency degradation, and thermal stress can cause interlayer delamination and perovskite layer cracking. Third, continuous illumination, especially ultraviolet light, can induce perovskite lattice defects, further exacerbating device performance degradation.

[0004] To address the aforementioned issues, existing technologies primarily seek solutions from two aspects: encapsulation materials and thermal insulation structures. In terms of encapsulation, a sandwich structure of glass-encapsulant film-backsheet is used to isolate perovskite cells from water and oxygen. For example, POE (polyolefin elastomer) or PVB (polyvinyl butyral) is used as the encapsulant film to seal the cells between the front glass and the backsheet. Regarding thermal insulation, some technologies reduce the intake of solar heat radiation by depositing low-emissivity (Low-E) coatings or metallic reflective layers on the glass surface of the photovoltaic module. For instance, depositing an Ag film on the front glass surface to reflect far-infrared heat radiation, or incorporating a hollow layer to block heat conduction.

[0005] However, existing technologies still have the following shortcomings: Existing heat insulation methods (such as Low-E glass) are mostly passive blocking methods, which significantly affect visible light transmittance, and the heat insulation effect cannot be dynamically enhanced at high temperatures, making it difficult to cope with extreme high temperatures in summer. In existing technologies, the heat dissipation structure and the packaging structure are independent of each other, lacking coordinated design, resulting in limited heat dissipation efficiency and difficulty in effectively dissipating heat from inside the component. Summary of the Invention

[0006] To address the problems of "interlayer delamination and perovskite layer cracking caused by thermal stress, efficiency degradation and shortened lifespan due to high-temperature operation, and material decomposition and ion migration induced by ultraviolet light irradiation" in existing technologies, this invention provides a flexible perovskite photovoltaic building material and its preparation method. By sequentially depositing a graphene-alumina composite film, a V-transparent conductive oxide film, and a silicon nitride layer on the surface of the front glass, an integrated composite film layer with ultra-high water and oxygen barrier properties and rapid in-plane heat dissipation is constructed.

[0007] Specifically, the present invention provides a flexible perovskite photovoltaic building material, including a building material substrate and a flexible perovskite photovoltaic module bonded to the surface of the building material substrate. The flexible perovskite photovoltaic module includes a perovskite photovoltaic cell, a front glass panel, and a composite film layer disposed on the surface of the front glass panel facing the perovskite photovoltaic cell. The composite film layer is bonded to the perovskite photovoltaic cell. The composite film layer includes a graphene alumina composite film layer, a transparent conductive oxide film layer, and a silicon nitride layer sequentially deposited on the surface of the front glass panel facing the cell.

[0008] This invention constructs a three-layer composite film structure consisting of a graphene-alumina composite film, a transparent conductive oxide film, and a silicon nitride layer on the side of the front glass facing the battery cell, forming an integrated "heat dissipation-conductivity-barrier" functional unit.

[0009] The atomic-level thickness of the graphene layer endows it with excellent flexibility, allowing it to absorb strain through in-plane lattice slip and wrinkle deformation when bent, preventing stress from being transferred to the upper brittle film layer. The alumina layer, as an ultra-thin and dense layer deposited at atomic levels, precisely fills the grain boundaries of graphene, transferring wrinkles and defects. At the same time, the graphene-alumina composite film layer has both ultra-high in-plane thermal conductivity and atomic-level water and oxygen barrier functions, rapidly spreading the heat generated by the solar cell along the planar direction to eliminate hot spots, while the alumina fills the graphene grain boundary defects to form a dense barrier. The transparent conductive oxide film layer acts as an electrode to collect photogenerated carriers, and its free carriers can reflect some near-infrared thermal radiation to reduce heat absorption by the module. The silicon nitride layer, as the innermost protective layer, provides dense chemical and physical protection. The three-layer structure synergistically solves the technical problem of the independent and lacking integration of heat dissipation, barrier and conductivity functions in the existing technology.

[0010] Preferably, the graphene-alumina composite film layer includes a graphene layer and an alumina layer atomically deposited on the graphene layer, wherein the thickness of the graphene layer is 10-30 nm and the thickness of the alumina layer is 10-20 nm.

[0011] Preferably, the transparent conductive oxide film is a single-layer tin-doped indium oxide film, a fluorine-doped tin oxide film, or an aluminum-doped zinc oxide film, and the thickness of the transparent conductive oxide film is 100-300 nm.

[0012] Preferably, the transparent conductive oxide film layer is doped with Nanoparticles, the The doping amount of the nanoparticles is 3-5 wt% of the total mass of the transparent conductive oxide film. Utilizing... The wide-bandgap semiconductor characteristic absorbs ultraviolet light with wavelengths <380nm, blocking it outside the perovskite layer, thus solving the problem of ultraviolet light-induced organic cations in perovskite. The problems include bond breaking and lattice degradation.

[0013] Preferably, it is prepared by the following steps: co-sputtering a transparent conductive oxide target and a titanium target, wherein the sputtering atmosphere is... and A mixture of gases, in which Volume fraction 3-8%, substrate temperature 200-350°C, controlled by adjusting titanium vanadium target sputtering power. The doping amount is 3-5 wt%, after sputtering Anneal at 400-420°C for 30-60 minutes in an atmosphere.

[0014] Preferably, the thickness of the silicon nitride layer is 50-100 nm.

[0015] This invention also provides a method for preparing the above-mentioned flexible perovskite photovoltaic building material, comprising the following steps: A graphene layer and an aluminum oxide layer are sequentially deposited on the surface of the front glass facing the perovskite photovoltaic cell to form a graphene-alumina composite film. Then, a transparent conductive oxide film and a silicon nitride layer are sequentially deposited on the graphene-alumina composite film. Perovskite solar cells are bonded to a building material substrate to obtain a perovskite solar cell module. The front glass with the composite film deposited thereon is bonded and pressed together with the perovskite photovoltaic cell module to obtain flexible perovskite photovoltaic building material.

[0016] The preparation method provided by the present invention involves sequentially depositing three composite film layers on the front glass and then bonding and pressing them with the perovskite solar cell and building material substrate. This separates the preparation of the functional film layer on the front glass side from the assembly of the module into two independent process stages, thereby improving process compatibility and yield.

[0017] Preferably, the graphene layer is deposited by CVD, the alumina layer is deposited by atomic layer deposition, the transparent conductive oxide film layer is deposited by magnetron sputtering, and the silicon nitride layer is deposited by PECVD.

[0018] Preferably, before depositing the alumina layer, the graphene layer is pretreated with ozone at a flow rate of 50-200 sccm, a temperature of 80-150°C, and a treatment time of 1-5 minutes. The strong oxidizing properties of ozone gently introduce oxygen-containing active groups such as hydroxyl and epoxy groups onto the graphene surface. These oxygen-containing groups act as… The chemical nucleation sites enable the alumina nucleation density on the graphene surface to be increased, ensuring that the alumina layer can completely cover all grain boundaries and defects of graphene, achieving a dense barrier without pinholes.

[0019] Preferably, before depositing the silicon nitride layer, the surface of the transparent conductive oxide film layer is subjected to... Plasma treatment, RF power 50-150W, cavity pressure 20-100Pa, substrate temperature 100-150°C. Flow rate 100-300 sccm, processing time 1-5 minutes.

[0020] pass Plasma treatment removes surface hydrocarbon contaminants and repairs oxygen vacancy defects. Simultaneously, N radicals react in situ with metal atoms on the TCO surface to generate a metal nitride transition layer. The lattice constant of this transition layer is between that of the oxide TCO and the nitride SiNx, eliminating interfacial lattice abrupt changes and enabling SiNx to form a dense and continuous film. This improves interlayer adhesion and reduces water and oxygen permeability.

[0021] More preferably, before depositing the silicon nitride layer, the... The surface of the doped transparent conductive oxide film is subjected to Plasma treatment, active nitrogen atoms in the plasma and In-situ generation of surface reaction , The density is higher than Furthermore, the ultraviolet photocatalytic activity was suppressed by 50-70%, eliminating... Risk of photocatalytic degradation of perovskite.

[0022] The present invention has the following beneficial effects: A three-layer integrated composite film structure consisting of a graphene-alumina composite film, a transparent conductive oxide film, and a silicon nitride layer is constructed on the side of the front glass facing the solar cell. The graphene layer, with its atomic-level flexibility, absorbs strain through in-plane lattice slip during bending, while the alumina layer buffers thermal mismatch stress through CTE gradient matching. Together, they reduce interlayer delamination and perovskite layer cracking caused by thermal stress. The ultra-high in-plane thermal conductivity of graphene rapidly spreads the heat generated by the solar cell horizontally, eliminating hot spots. Simultaneously, the free carrier pairs of the transparent conductive oxide film... Near-infrared thermal radiation generates reflection, reducing heat absorption by the module. The two work together to lower the module's operating temperature compared to existing technologies, effectively suppressing efficiency degradation and shortened lifespan caused by high temperatures. The alumina layer fills the graphene grain boundary defects to form a dense water and oxygen barrier, which, together with the silicon nitride layer, constitutes a dual protection, blocking water, oxygen, and moisture that induce ion migration outside the perovskite layer. At the same time, the graphene / alumina composite layer has a certain absorption capacity for ultraviolet light, which, together with the ultraviolet absorber contained in the front glass body, reduces material decomposition and ion migration induced by ultraviolet light irradiation.

[0023] Other features and advantages of the invention will be set forth in the following description, and will be apparent in part from the description, or may be learned by practicing the invention. The objects and other advantages of the invention may be realized and obtained by means of the structures particularly pointed out in the written description and the accompanying drawings.

[0024] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description

[0025] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used in conjunction with embodiments of the invention to explain the invention and do not constitute a limitation thereof. In the drawings: Figure 1 This is a schematic flowchart illustrating a method for preparing a flexible perovskite photovoltaic building material according to the present invention. Detailed Implementation

[0026] The preferred embodiments of the present invention will be described below with reference to the accompanying drawings. It should be understood that the preferred embodiments described herein are for illustration and explanation only and are not intended to limit the present invention.

[0027] This invention provides a flexible perovskite photovoltaic building material, including a building material substrate and a flexible perovskite photovoltaic module bonded to the surface of the building material substrate. The flexible perovskite photovoltaic module includes a perovskite photovoltaic cell, a front glass panel, and a composite film layer disposed on the surface of the front glass panel facing the perovskite photovoltaic cell. The composite film layer is bonded to the perovskite photovoltaic cell. The composite film layer includes a graphene-alumina composite film layer, a transparent conductive oxide film layer, and a silicon nitride layer sequentially deposited on the surface of the front glass panel facing the cell.

[0028] The present invention will be further described below with reference to embodiments.

[0029] The following performance tests were conducted in the following examples. (1) Thermal cycling test (IEC 61215 MQT 11, -40°C to 85°C, 200 cycles), the resistance to thermal stress cracking and interlayer delamination was verified by visual inspection (no cracks, no bubbles, no delamination) and power attenuation ≤5%; (2) Ultraviolet aging test, the UV protection and resistance to photodegradation were verified by efficiency attenuation ≤10% and UV-Vis spectrum (300-400nm transmittance ≤5%); (3) Water and oxygen transmittance test (ASTM F1249, Mocon method, target (3) Verify the blocking effect of the composite membrane on water and oxygen intrusion and ion migration channels; (4) Comparative test of working temperature to verify the effect of graphene in-plane thermal conductivity on high-temperature efficiency decay.

[0030] like Figure 1 As shown, the present invention also provides a method for preparing the above-mentioned flexible perovskite photovoltaic building material, comprising the following steps: A graphene layer and an aluminum oxide layer are sequentially deposited on the surface of the front glass facing the perovskite photovoltaic cell to form a graphene-alumina composite film. Then, a transparent conductive oxide film and a silicon nitride layer are sequentially deposited on the graphene-alumina composite film. Perovskite solar cells are bonded to a building material substrate to obtain a perovskite solar cell module. The front glass with the composite film deposited thereon is bonded and pressed together with the perovskite photovoltaic cell module to obtain flexible perovskite photovoltaic building material.

[0031] Example 1

[0032] This embodiment sets up three sets of experiments: Group 1: Graphene layer thickness 10nm, alumina layer thickness 10nm, TCO layer thickness 100nm, silicon nitride layer thickness 50nm. Group 2: Graphene layer thickness 20nm, alumina layer thickness 15nm, TCO layer thickness 200nm, silicon nitride layer thickness 75nm. The preparation steps are the same as Group 1, only the corresponding deposition thickness and deposition time are adjusted. Group 3: Graphene layer thickness 30nm, alumina layer thickness 20nm, TCO layer thickness 300nm, silicon nitride layer thickness 100nm.

[0033] Table 1

[0034] The test results are shown in Table 1. It can be seen that Group 2 performs best in terms of in-plane thermal conductivity (14.8 W / m·K), thermal cycling stability (power attenuation of 2.1%), UV protection (transmittance of 3.5%), and heat dissipation effect (temperature reduction of 11.2°C), and is determined to be the preferred parameter combination for the basic structure of the composite film layer of this invention.

[0035] Example 2

[0036] This embodiment sets up two sets of experiments. Set 1: Magnetron co-sputtering using ITO and titanium targets, with a sputtering atmosphere of... and Mixed gas ( (volume fraction 5%), substrate temperature 280°C, controlled by adjusting titanium target sputtering power. The doping concentration was 3 wt%, and after sputtering, it was annealed at 410°C for 45 minutes in an N2 atmosphere to form... A transparent conductive oxide film doped with ITO was prepared. The remaining preparation steps were the same as in Example 1, Group 2. Group 2: The preparation steps were the same as in Group 2, except that the sputtering power of the titanium target was adjusted. The doping level was increased to 5 wt%.

[0037] Table 2

[0038] The test results are shown in Table 2. It can be seen that the efficiency of group 2 decreased by 4.5% after UV aging, the transmittance of the UV-Vis spectrum in the 300-400 nm range was 1.8%, and the WVTR was [missing value]. After thermal cycling, the power decay was 2.5%, and the operating temperature was 10.5°C lower than the control group. Group 2 (5wt% doping) showed better performance in terms of UV protection (efficiency decay of only 4.5%, and transmittance of only 1.8% in the 300-400nm range), and was thus identified as the present invention. Preferred values ​​for doping concentration.

[0039] Example 3

[0040] This embodiment sets up two sets of experiments. Set 1: The CVD-deposited graphene layer is pretreated with ozone at a flow rate of 50 sccm, a temperature of 80°C, and a treatment time of 1 minute. Subsequently, an alumina layer (15 nm thick) is deposited using the ALD method. The remaining preparation steps are the same as in Set 2 of Example 1. Set 2: The CVD-deposited graphene layer is pretreated with ozone at a flow rate of 200 sccm, a temperature of 150°C, and a treatment time of 5 minutes. Subsequently, an alumina layer (15 nm thick) is deposited using the ALD method. The remaining preparation steps are the same as in Set 2 of Example 1.

[0041] Table 3

[0042] The test results are shown in Table 3. It is evident that the ozone pretreatment in Group 2 (5-minute treatment) fully activated the graphene surface, resulting in a higher density of the alumina layer and a reduction in WVTR. The stability of thermal cycling and ultraviolet aging is significantly improved, and it is determined to be the preferred value of ozone pretreatment time in this invention.

[0043] Example 4

[0044] This embodiment sets up four groups of experiments. Group 1: In the TCO layer (200nm ITO, without...) (Doped) surface Plasma treatment, RF power 50W, cavity pressure 20Pa, substrate temperature 100°C. The flow rate was 100 sccm, the processing time was 1 minute, and the remaining preparation steps were the same as in Example 1, Group 2.

[0045] Group 2: On the surface of the TCO layer (200nm ITO, without TiO2 doping) Plasma treatment, RF power 150W, cavity pressure 100Pa, substrate temperature 150°C. The flow rate was 150 sccm, the processing time was 1 minute, and the remaining preparation steps were the same as in Example 1, Group 2.

[0046] Group 3: On the surface of the TCO layer (200nm ITO, without TiO2 doping) Plasma treatment, RF power 100W, cavity pressure 60Pa, substrate temperature 120°C The flow rate was 200 sccm, the processing time was 1 minute, and then a silicon nitride layer (75 nm thick) was deposited by PECVD. The remaining preparation steps were the same as in Example 1, Group 2.

[0047] Group 4: In The surface of the doped (4wt%) TCO layer was subjected to... Plasma treatment, the process is the same as group 3 of this embodiment.

[0048] Table 4

[0049] The test results are shown in Table 4. It is evident that group 3 exhibits the best overall performance among the undoped TCO schemes, and is therefore selected as the appropriate scheme for this invention. Preferred process parameters for plasma treatment (100W / 60Pa / 1min). Group 4 Doping and The synergistic effect of plasma treatment resulted in an efficiency decrease (4.2%) after UV aging and a reduction in WVTR. In terms of both thermal cycling stability (1.8%), it is superior to the undoped group 3 (6.5%). (2.0%), proof Doping and Plasma treatment has a significant synergistic enhancement effect.

[0050] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from its spirit and scope. Therefore, if these modifications and variations fall within the scope of the claims of this invention and their equivalents, this invention also intends to include these modifications and variations.

Claims

1. A flexible perovskite photovoltaic building material, characterized in that, The invention includes a building material substrate and a flexible perovskite photovoltaic module bonded to the surface of the building material substrate. The flexible perovskite photovoltaic module includes a perovskite photovoltaic cell, a front glass panel, and a composite film layer disposed on the surface of the front glass panel facing the perovskite photovoltaic cell. The composite film layer is bonded to the perovskite photovoltaic cell. The composite film layer includes a graphene-alumina composite film layer, a transparent conductive oxide film layer, and a silicon nitride layer sequentially deposited on the surface of the front glass panel facing the cell.

2. The flexible perovskite photovoltaic building material according to claim 1, characterized in that, The graphene-alumina composite film includes a graphene layer and an alumina layer atomically deposited on the graphene layer. The thickness of the graphene layer is 10-30 nm, and the thickness of the alumina layer is 10-20 nm.

3. The flexible perovskite photovoltaic building material according to claim 1, characterized in that, The transparent conductive oxide film is a single-layer tin-doped indium oxide film, a fluorine-doped tin oxide film, or an aluminum-doped zinc oxide film, and the thickness of the transparent conductive oxide film is 100-300 nm.

4. The flexible perovskite photovoltaic building material according to claim 1, characterized in that, The transparent conductive oxide film layer is doped with Nanoparticles, the The amount of nanoparticles doped is 3-5 wt% of the total mass of the transparent conductive oxide film.

5. The flexible perovskite photovoltaic building material according to claim 4, characterized in that, The material was prepared by the following steps: co-sputtering a transparent conductive oxide target and a titanium target under a sputtering atmosphere of [insert sputtering atmosphere here]. and A mixture of gases, in which Volume fraction 3-8%, substrate temperature 200-350°C, controlled by adjusting titanium vanadium target sputtering power. The doping amount is 3-5 wt%, after sputtering Anneal at 400-420°C for 30-60 minutes in an atmosphere.

6. The flexible perovskite photovoltaic building material according to claim 1, characterized in that, The thickness of the silicon nitride layer is 50-100 nm.

7. A method for preparing the flexible perovskite photovoltaic building material according to any one of claims 1-6, characterized in that, Includes the following steps: A graphene layer and an aluminum oxide layer are sequentially deposited on the surface of the front glass facing the perovskite photovoltaic cell to form a graphene-alumina composite film. Then, a transparent conductive oxide film and a silicon nitride layer are sequentially deposited on the graphene-alumina composite film. Perovskite solar cells are bonded to a building material substrate to obtain a perovskite solar cell module. The front glass with the composite film deposited thereon is bonded and pressed together with the perovskite photovoltaic cell module to obtain flexible perovskite photovoltaic building material.

8. The preparation method according to claim 7, characterized in that, The graphene layer was deposited using CVD, the alumina layer was deposited using atomic layer deposition, the transparent conductive oxide film layer was deposited using magnetron sputtering, and the silicon nitride layer was deposited using PECVD.

9. The preparation method according to claim 7, characterized in that, Before depositing the alumina layer, the graphene layer is pretreated with ozone at a flow rate of 50-200 sccm, a temperature of 80-150°C, and a treatment time of 1-5 minutes.

10. The preparation method according to claim 5, characterized in that, Before depositing the silicon nitride layer, the surface of the transparent conductive oxide film layer is subjected to... Plasma treatment, RF power 50-150W, cavity pressure 20-100Pa, substrate temperature 100-150°C. Flow rate 100-300 sccm, processing time 1-5 minutes.

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