A general analysis method for identifying the whitening of the film surface of a perovskite photovoltaic module

Abstract

This invention relates to the field of perovskite solar cell technology, specifically to a general analytical method for identifying whitening of the perovskite photovoltaic module film surface. The method includes: (a) laminating a first assembly formed by a silicone layer, a first adhesive layer, a first bottom glass, and a first cover glass to obtain the lamination process conditions corresponding to no contact between the first cover glass and the silicone layer after lamination; (b) using the lamination process conditions of step (a), laminating a second assembly formed by a perovskite module base layer, a support frame, a second adhesive layer, a second bottom glass, and a second cover glass to obtain a perovskite photovoltaic module; (c) after confirming the perovskite photovoltaic module is qualified, powering it on until whitening appears on the film surface, obtaining the whitened area, and performing detection and analysis. This method avoids damage to the film layer, allows for more accurate and intuitive analysis of the causes of whitening on the perovskite photovoltaic module film surface, and is highly efficient.

Description

Technical Field

[0001] This invention relates to the field of perovskite solar cell technology, and more specifically, to a general analytical method for identifying whitening of the film surface in perovskite photovoltaic modules. Background Technology

[0002] Perovskite, as a powerful emerging photovoltaic material, is considered a potential low-cost photovoltaic material to replace crystalline silicon due to its excellent photoelectric properties and high power conversion efficiency (PCE). Its printable and scratch-coated manufacturing methods have also significantly reduced the production and technological costs of perovskite photovoltaic modules. However, perovskite, despite its many advantages, also has several drawbacks. As an organic-inorganic mixed ionic crystal, perovskite is relatively soft, with weak valence bonds between elements, and its crystal growth is difficult to control. These drawbacks restrict the large-scale production of perovskite photovoltaic modules. Furthermore, perovskite is highly susceptible to decomposition under external pressure. For example, when a reverse (forward) bias voltage is applied to the module, the impact of a strong current accelerates the decomposition and yellowing of perovskite, leading to rapid failure of the photovoltaic module.

[0003] After continuous process upgrades and optimizations, the conversion efficiency of perovskite photovoltaic (PV) devices with single-junction heterojunction structures has become comparable to that of crystalline silicon PV devices with the same structure. However, due to the lack of a clearly defined system for perovskite PV modules with specific aging procedures, testing frameworks, and test sequences, stability certification for perovskite PV modules still follows the existing IEC 61215 PV module testing standard. According to the stability test sequence requirements given in the IEC 61215 stability test sequence document, perovskite PV modules need to undergo standard aging tests such as DH (damp heat) and TC (thermal cycling). However, during the actual testing process, perovskite PV modules have experienced module failures within a short period. One notable failure is the whitening of the film surface after TC energization, a failure not observed in other PV modules. As a unique failure characteristic of perovskite PV modules, the degree of whitening is closely related to module performance. Furthermore, due to the specificity and uniqueness of this failure, no effective analytical method has yet been proposed to specifically diagnose the mechanism of this phenomenon.

[0004] In current photovoltaic module failure analysis techniques, there is still a lack of methods for reproducing and analyzing the whitening of the film surface after aging in perovskite photovoltaic modules. As an ionic crystal, perovskite's atomic valence bonds are not as strong as the covalent bonds between elements in crystalline silicon. This causes perovskite modules to fail to withstand reverse electrophoresis or applied voltage in the IEC61215 aging sequence. When perovskite modules are powered on, the poor intrinsic electrical stability of perovskite is exposed by the influence of ambient temperature (-40℃-85℃), leading to module failure. To perform failure analysis on components, it is often necessary to peel off the film layers of the perovskite module of the thin-film device. However, the "sandwich" structure of the perovskite module includes a polyolefin elastomer (POE) film used for encapsulation. The POE fused to the Cu electrode and the back glass are bonded together. When the back glass and the bottom film layer are forcibly separated, damage to the film layer is inevitable. However, there is currently no method for non-destructive analysis of the whitening film layer of perovskite. This increases the difficulty of low-damage or non-destructive analysis of perovskite thin films. Moreover, given that the thickness of thin-film perovskite is less than the micrometer level, this also requires higher precision testing equipment, which often leads to increased testing costs and an increased error rate in sample preparation, which is not in line with the company's business philosophy of improving efficiency and reducing costs.

[0005] In view of this, the present invention is hereby proposed. Summary of the Invention

[0006] One objective of this invention is to provide a universal analytical method for identifying whitening of the film surface in perovskite photovoltaic modules. This method is characterized by low cost, low sample preparation error rate, high efficiency, and universality, and can greatly improve the efficiency of module failure analysis.

[0007] In order to achieve the above-mentioned objectives of the present invention, the following technical solution is adopted:

[0008] A general analytical method for identifying whitening of the perovskite photovoltaic module film surface includes the following steps:

[0009] (a) The first assembly formed by the silicone layer, the first adhesive layer, the first bottom glass and the first cover glass is laminated and tested to obtain the lamination process conditions corresponding to the first cover glass and the silicone layer having no contact after lamination.

[0010] (b) Using the lamination process conditions of step (a), the second assembly formed by the perovskite module base layer, support frame, second adhesive layer, second bottom glass and second cover glass is laminated to obtain a perovskite photovoltaic module;

[0011] (c) After confirming that the perovskite photovoltaic module is qualified, an aging process is performed until the perovskite photovoltaic module shows white film on the surface. The white film area is then obtained and detected and analyzed.

[0012] In one embodiment, the silicone-containing layer includes at least one of a silicone film layer and a polydimethylsiloxane film layer.

[0013] In one embodiment, the Shore hardness of the silicone layer is 5 to 20.

[0014] In one embodiment, the thickness of the silicone layer is ≤5μm.

[0015] In one embodiment, in the first assembly, the first cover glass and the first bottom glass are arranged face to face; one side surface of the silicone layer is connected to the first bottom glass, and the other side surface faces away from the first cover glass; the first cover glass and the first bottom glass are connected by the first adhesive layer, and the first adhesive layer surrounds the silicone layer.

[0016] In one embodiment, the thickness of the first adhesive layer is 0.5 to 0.9 mm.

[0017] In one embodiment, both the first cover glass and the first bottom glass are non-tempered glass with a thickness of 2.2 to 10 mm.

[0018] In one embodiment, the lamination process conditions in step (a) include: vacuuming, first-stage pressure holding, second-stage pressure holding, and lamination.

[0019] In one embodiment, in the second assembly, the second bottom glass and the second cover glass are arranged face to face; one side surface of the perovskite module base layer is connected to the second bottom glass, and the other side surface faces and is separate from the second cover glass; the second bottom glass and the second cover glass are connected by a second adhesive layer, and the second adhesive layer surrounds the perovskite module base layer; the support frame is located between the perovskite module base layer and the second cover glass, and the support frame is connected to the perovskite module base layer.

[0020] In one embodiment, along the direction from the second bottom glass to the second cover glass, the perovskite module base layer sequentially includes a transparent electrode layer, a first charge transport layer, a perovskite film layer, a second charge transport layer, and a back electrode layer.

[0021] In one embodiment, the perovskite module base layer further includes a barrier layer.

[0022] In one embodiment, the thickness of the second adhesive layer is 0.5 to 0.9 mm.

[0023] In one embodiment, the shape of the support frame includes at least one of dot-shaped, line-shaped, and grid-shaped.

[0024] In one embodiment, the support frame is made of at least one of POE, PVB, PIB, and PTFE.

[0025] In one embodiment, the thickness of the support frame in the perovskite photovoltaic module is 200–1000 μm.

[0026] In one embodiment, the first cover glass and the second cover glass are made of the same material and have the same thickness;

[0027] The first and second bottom glass panels are made of the same material and have the same thickness;

[0028] The first adhesive layer and the second adhesive layer are made of the same material and have the same thickness;

[0029] The silicone-containing layer has the same thickness as the perovskite module base layer.

[0030] In one embodiment, the aging process includes electrical aging.

[0031] In one implementation, the qualified perovskite photovoltaic module is subjected to a power test before being powered on.

[0032] In one embodiment, in step (c), the whitened area of ​​the perovskite photovoltaic module is obtained by disassembling and cutting the whitened area; the whitened area is then subjected to SEM detection and analysis.

[0033] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0034] This invention provides a universal analytical method for identifying whitening on the surface of perovskite photovoltaic modules. The sampling method is simple and can restore the whitening phenomenon of perovskite modules without damage. It is easy to operate and has very low equipment requirements. It can analyze the causes of whitening on the surface of perovskite photovoltaic modules more accurately and intuitively, and greatly improve the efficiency of module failure analysis. Attached Figure Description

[0035] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0036] Figure 1 This is a schematic diagram of the main cross-sectional structure of the first assembly of the present invention;

[0037] Figure 2 A schematic diagram of the main cross-sectional structure of the second assembly of the present invention;

[0038] Figure 3 This is a JV performance test diagram of the perovskite solar cell module of Embodiment 1 of the present invention;

[0039] Figure 4 This is a whitening image of the perovskite solar cell module according to Embodiment 1 of the present invention.

[0040] Figure 5 This is a scanning electron microscope image of the whitened area on the film surface of the perovskite solar cell module in Embodiment 1 of the present invention.

[0041] Figure label:

[0042] 1-First cover glass, 2-First bottom glass, 3-First adhesive layer, 4-Silicone layer, 5-Second cover glass, 6-Second bottom glass, 7-Perovskite module base layer, 8-Second adhesive layer, 9-Support frame. Detailed Implementation

[0043] The embodiments of the present invention will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are only for illustrating the present invention and should not be considered as limiting the scope of the present invention. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer are followed. Instruments used without specified manufacturers are all commercially available conventional products. In the description of the present invention, it should be noted that the terms "first" and "second" are only used for distinguishing descriptions and should not be construed as indicating or implying relative importance.

[0044] According to one aspect of the present invention, the present invention relates to a general analytical method for identifying whitening of the film surface of a perovskite photovoltaic module, comprising the following steps:

[0045] (a) The first assembly formed by the silicone layer, the first adhesive layer, the first bottom glass and the first cover glass is laminated and tested to obtain the lamination process conditions corresponding to the first cover glass and the silicone layer having no contact after lamination.

[0046] (b) Using the lamination process conditions of step (a), the second assembly formed by the perovskite module base layer, support frame, second adhesive layer, second bottom glass and second cover glass is laminated to obtain a perovskite photovoltaic module;

[0047] (c) After confirming that the perovskite photovoltaic module is qualified, an aging process is performed until the perovskite photovoltaic module shows white film on the surface. The white film area is then obtained and detected and analyzed.

[0048] Due to the inherent brittleness and flexibility of glass, to avoid damage to the film structure caused by the pressure exerted by the cover glass on the lower film layer, a support frame is needed to isolate the cover glass and the lower film layer. Before determining the layout of the support frame, the lamination process is adjusted in advance using the silicone layer area contact method. By continuously adjusting and optimizing the lamination process parameters, the cover glass and the lower silicone layer have no contact surface; thus, the lamination process conditions are determined. The perovskite module base layer, support frame, second adhesive layer, second bottom glass, and second cover glass are assembled to form a second assembly. The support frame is laid out according to the pre-determined lamination process conditions, using step (a). The lamination process is performed to obtain the perovskite photovoltaic module. The absence of a POE adhesive layer is to prevent POE adhesive from peeling off the Cu electrode surface during the later separation of the cover glass and the underlying film, which would damage the film and hinder in-situ observation of the perovskite core film layers. Additionally, due to the deflection of the cover glass, it may press against the perovskite module base layer, causing film damage. Therefore, a support frame is used to prevent damage to the film layers of the perovskite module base layer. After confirming the perovskite photovoltaic module is qualified, an aging treatment is performed until the perovskite photovoltaic module film surface turns white. The whitened area is then collected and analyzed.

[0049] In one embodiment, the silicone layer comprises at least one of a silicone film layer and a polydimethylsiloxane film layer. The silicone film layer uses conventional industrial molding silicone, and the colloid is divided into A and B components. Component A is the silicone adhesive, and component B is the curing agent. In one embodiment, a mixture of equal masses of A and B components is stirred and vacuum-treated to form a transparent colloid. This colloid is then coated using a scraper to form a transparent, smooth film, followed by curing. During the stirring process, numerous small air bubbles are generated within the colloid. These bubbles are detrimental to subsequent film formation; therefore, vacuum treatment is used to remove the air bubbles from the colloid, resulting in a transparent colloid. In one embodiment, after film preparation, it needs to be cured in an environment with a humidity ≥40% (e.g., 40%–100%, e.g., 50%, 60%, 70%, 80%) for at least 6 hours, e.g., 6–24 hours, e.g., 7 hours, 8 hours, 10 hours, 15 hours, etc. The film surface needs to be smooth, with a flatness within 100 μm, e.g., 10–95 μm. In one embodiment, the thickness of the silicone-containing layer is ≤5μm, such as 1μm, 1.5μm, 2μm, 2.5μm, 3μm, 3.5μm, 4μm, 4.5μm, or 5μm. In another embodiment, the Shore hardness of the film is 5–20, such as 5, 8, 10, 12, 15, 16, or 18. If the Shore hardness is too low, the lamination will arch when heated, affecting the identification of the contact surface. The main function of the silicone-containing layer in this invention is to simulate perovskite films; since PDMS is relatively expensive, this invention preferably uses a silicone film layer. In one specific embodiment, a mixture of equal masses of adhesive A and adhesive B is stirred and vacuum-treated to form a transparent colloid. This colloid is then coated onto a first substrate glass using a scraper to form a transparent, flat film, followed by curing. The curing humidity is 50%, and the curing time is 7 hours.

[0050] In one embodiment, in the first assembly, the first cover glass and the first bottom glass are arranged face to face; one side surface of the silicone-containing layer is connected to the first bottom glass, and the other side surface faces away from and away from the first cover glass; the first cover glass and the first bottom glass are connected by a first adhesive layer, and the first adhesive layer surrounds the silicone-containing layer. In one embodiment, the thickness of the first adhesive layer is 0.5–0.9 mm, for example 0.7 mm, 0.8 mm, 0.82 mm, etc., and the material includes butyl rubber (PIB). In one embodiment, both the first cover glass and the first bottom glass are non-tempered glass, and their thicknesses are both 2.2–10 mm, for example 3 mm, 4 mm, 5 mm, 6 mm, etc.

[0051] In one embodiment, the lamination process conditions in step (a) include: vacuuming, primary pressure holding, secondary pressure holding, and lamination; the vacuuming time is 350–450 s, for example, 400 s, 420 s, etc.; the primary pressure holding pressure is -75–-85 kPa, for example, -80 kPa, and the primary pressure holding time is 250–350 s, for example, 280 s, 300 s, 330 s, etc.; the secondary pressure holding pressure is -55–-65 kPa, for example, -60 kPa, and the secondary pressure holding time is 550–650 s, for example, 580 s, 600 s, 620 s, etc.; the lamination time is 2–5 s, for example, 3 s, 4 s, etc.; the lamination pressure is 55–65 kPa, for example, 60 kPa; and the lamination temperature is 95–120°C, for example, 98°C, 100°C, 110°C, etc.

[0052] In one embodiment, in the second assembly, the second bottom glass and the second cover glass are arranged face to face; one side surface of the perovskite module base layer is connected to the second bottom glass, and the other side surface faces and is separate from the second cover glass; the second bottom glass and the second cover glass are connected by a second adhesive layer, and the second adhesive layer surrounds the perovskite module base layer; the support frame is located between the perovskite module base layer and the second cover glass, and the support frame is connected to the perovskite module base layer.

[0053] In one embodiment, the shape of the support frame includes at least one of dot-like, line-like, and grid-like shapes. The dot-like shape includes at least one of regular and irregular shapes; the regular shape includes at least one of circles, ellipses, triangles, and regular polygons. In one embodiment, the dot-like support frames are uniformly distributed in the central region of the upper surface of the perovskite module base layer. The line-like shape includes at least one of straight and curved shapes. The grid-like shape includes: a support frame base and a plurality of through holes disposed on the support frame base; the through holes are arranged in an array; in one embodiment, the shape of the through holes includes at least one of regular and irregular shapes, the regular shape including at least one of circles, ellipses, triangles, and regular polygons. In one embodiment, the material of the support frame includes at least one of POE, PVB (polyvinyl butyral), PIB, and PTFE (polytetrafluoroethylene). In one embodiment, the thickness of the laminated support frame is 200–1000 μm, such as 300 μm, 400 μm, 500 μm, 600 μm, 650 μm, 680 μm, 700 μm, 750 μm, 800 μm, 900 μm, 1000 μm, etc. In this invention, it is necessary to minimize the effective area occupied by the support frame while ensuring contact between the insulating back glass and the bottom film surface, and to minimize the impact of the contact area of ​​the support frame on the film surface.

[0054] In one embodiment, along the direction from the second bottom glass to the second cover glass, the perovskite module base layer sequentially includes a transparent electrode layer, a first charge transport layer, a perovskite film layer, a second charge transport layer, and a back electrode layer. In one embodiment, the transparent electrode layer is an FTO layer. The thickness of the transparent electrode layer is 1.8–2.2 mm, for example, 1.9 mm, 2 mm, etc. In one embodiment, the first charge transport layer includes NiO. x That is, NiO2 and Ni2O3. In one embodiment, the thickness of the first charge transport layer is 30-50 nm, such as 35 nm, 40 nm, 45 nm, etc. In one embodiment, the perovskite film layer includes a PVSK layer with a thickness of 400-450 nm, such as 410 nm, 420 nm, 430 nm, 450 nm, etc. In one embodiment, the second charge transport layer includes C 60 The second charge transport layer has a thickness of 20–40 nm, such as 25 nm, 30 nm, or 35 nm. In one embodiment, C... 60 The thickness of the layer is 15–25 nm, for example, 18 nm, 20 nm, etc.; the thickness of the SnO2 layer is 5–15 nm, for example, 8 nm, 10 nm, 12 nm. In one embodiment, the back electrode layer includes a Cu layer; in another embodiment, the thickness of the back electrode layer is 15–25 nm, for example, 18 nm, 20 nm, 22 nm, etc. In one embodiment, the perovskite module base layer further includes a barrier layer. In one embodiment, the barrier layer includes a BCP layer. In another embodiment, the thickness of the barrier layer is 60–80 nm. In another embodiment, the thickness of the second adhesive layer is 0.5–0.9 mm, for example, 0.7 mm, etc., and the material includes butyl rubber.

[0055] In one embodiment, both the second cover glass and the second bottom glass are non-tempered glass with a thickness of 2.2 to 10 mm, such as 3 mm, 4 mm, 5 mm, 6 mm, etc.

[0056] In one embodiment, the first cover glass and the second cover glass are made of the same material and have the same thickness; the first bottom glass and the second bottom glass are made of the same material and have the same thickness; the first adhesive layer and the second adhesive layer are made of the same material and have the same thickness. In one embodiment, the silicone-containing layer has the same thickness as the perovskite module base layer.

[0057] In one embodiment, the aging treatment includes power-on aging. In one embodiment, before power-on, a power test is performed on the qualified perovskite photovoltaic module. In one embodiment, in step (c), the perovskite photovoltaic module with a white film surface after disassembly and cutting is used to obtain the white film surface area; SEM detection and analysis are performed on the white film surface area.

[0058] In one embodiment, after the sample lamination is completed, an appearance inspection is performed on the sample protected by the support frame, and it is determined that there is no damage and color change in the non-support frame area after lamination. After determining that the sample is qualified, the sample is then transferred to the subsequent test. Before connecting the DC power supply, a power test needs to be performed on the sample, and then the sample is DC-powered. The specifications of the DC power supply meter need to be determined according to the J-V parameters measured by the sample. Specifically, the positive and negative lead-out wires of the test component are connected through alligator clips. Here, a constant voltage direct current is used. Before power-on, a voltage space of 1V is reserved, and then the power-on power is increased by adjusting the power-on current. When the current reaches the limit value, the voltage is adjusted, and the voltage is gradually increased in intervals of 0.5V / min until the voltage increases to the maximum power point voltage of the component. The maximum power point voltage and current of the component are obtained through the J-V performance test of the component. During the power-on process, the light-absorbing surface of the sample needs to be shielded from light to prevent the formation of photocurrent by light and the current generated by the power-on current from generating current counterflow and heating. This power-on process can be carried out at room temperature or in a TC environmental chamber until a white aggregation appears on the film surface, and then the power-on is stopped. In one embodiment, the power-on voltage cannot exceed 1.5 times of Vp, and the maximum power-on current cannot exceed 2.5 times of Jp.

[0059] In one embodiment, if the perovskite photovoltaic module is determined to be unqualified, the lamination process needs to be readjusted, the support frame is laid out, and then lamination is performed until a qualified perovskite photovoltaic module is obtained.

[0060] The following is an explanatory illustration with specific examples.

[0061] Example 1

[0062] A general analysis method for identifying the white film surface of a perovskite photovoltaic module includes the following steps:

[0063] (a) Assemble the silica gel layer 4, the first adhesive layer 3, the first bottom glass 2, and the first cover glass 1 to form a first assembly, as Figure 1 shown; then perform lamination debugging to obtain the lamination process conditions corresponding to no contact between the first cover glass 1 and the silica gel layer 4 after lamination;

[0064] In the first assembly, the first cover glass 1 and the first bottom glass 2 are arranged face to face; one side surface of the silicone layer 4 is connected to the first bottom glass 2, and the other side surface faces away from the first cover glass 1; the first cover glass 1 and the first bottom glass 2 are connected by the first adhesive layer 3, and the first adhesive layer 3 surrounds the silicone layer 4; the silicone layer 4 is a silicone film layer; the material of the first adhesive layer 3 is butyl rubber; the thickness of the silicone layer 4 is 592.2 nm, and the Shore hardness is 10. The thickness of the first adhesive layer 3 is 0.8 mm; the thickness of the first bottom glass 2 is 3.2 mm; and the thickness of the first cover glass 1 is 2.2 mm, all of which are non-tempered glass. The lamination process conditions include: vacuuming, first-stage pressure holding, second-stage pressure holding, and lamination. The vacuuming time is 400 s; the first-stage pressure holding pressure is -80 kPa, the first-stage pressure holding time is 300 s, the second-stage pressure holding pressure is -60 kPa, the second-stage pressure holding time is 600 s, the lamination time is 3 s, the lamination pressure is 60 kPa, and the lamination temperature is 100 ℃.

[0065] (b) Assemble the perovskite module base layer 7, support frame 9, second adhesive layer 8, second bottom glass 6, and second cover glass 5 to form a second assembly. The main cross-sectional view of the second assembly is shown in the figure below. Figure 2 As shown; using the lamination process conditions of step (a), the second assembly is laminated to obtain a perovskite photovoltaic module;

[0066] In the second assembly, the second bottom glass 6 and the second cover glass 5 are arranged face to face; one side surface of the perovskite module base layer 7 is connected to the second bottom glass 6, and the other side surface faces away from and away from the second cover glass 5; the second bottom glass 6 and the second cover glass 5 are connected by the second adhesive layer 8, and the second adhesive layer 8 surrounds the perovskite module base layer 7; the support frame 9 is located between the perovskite module base layer 7 and the second cover glass 5, and the support frame 9 is connected to the perovskite module base layer 7; along the direction from the second bottom glass 6 to the second cover glass 5, the perovskite module base layer 7 sequentially includes a transparent electrode layer, a first charge transport layer, a perovskite film layer (PVSK film), a second charge transport layer, a barrier layer, and a back electrode layer;

[0067] The support frame 9 is dot-shaped, with four dots connected sequentially to form a rectangle, located in the central region of the perovskite module base layer 7; the support frame 9 is made of PIB; after lamination, the thickness of the support frame 9 is 700 μm; the first charge transport layer is NiO. x The thickness is 40 nm; the thickness of the perovskite film is 430 nm; the second charge transport layer is C 60 Layer and SnO2 layer, C 60The thickness of the first layer is 20 nm, and the thickness of the SnO2 layer is 10 nm; the barrier layer is a BCP layer with a thickness of 70 nm; the back electrode layer is a Cu layer with a thickness of 20 nm; the transparent electrode layer is an FTO layer with a thickness of 2.2 mm; the thickness of the second adhesive layer 8 is 0.8 mm; the thickness of the second cover glass 5 is 2.2 mm, and the thickness of the second bottom glass 6 is 3.2 mm, all of which are non-tempered glass.

[0068] (c) Conduct an appearance inspection of the laminated perovskite photovoltaic module (sample) to ensure that there is no damage or discoloration in the non-support area after lamination. After confirming that the sample is qualified, transfer the sample to the later testing stage. Before connecting the DC power supply, the sample needs to be tested for power. Then, the sample is DC powered on. The DC power supply specification needs to be determined according to the JV parameters measured on the sample to determine the power supply range. During the power supply process, the light-absorbing surface of the sample needs to be protected from light to prevent the photocurrent and the current current from generating current collision and heating. This power supply process can be carried out at room temperature until the film surface shows white aggregation. Then, stop the power supply, disassemble and cut to obtain the white area on the film surface, complete the sample preparation according to the SEM sample preparation requirements, and then perform SEM detection and analyze the data.

[0069] The JV performance test chart of the perovskite solar cell module in this embodiment can be found in [reference needed]. Figure 3 .

[0070] Example 2

[0071] A general analytical method for identifying whitening of the perovskite photovoltaic module film surface includes the following steps:

[0072] (a) Assemble the silicone layer 4, the first adhesive layer 3, the first bottom glass 2, and the first cover glass 1 to form a first assembly, such as Figure 1 As shown; then perform lamination debugging to obtain the lamination process conditions corresponding to the first cover glass 1 and the silicone layer 4 having no contact after lamination;

[0073] In the first assembly, the first cover glass 1 and the first bottom glass 2 are arranged face to face; one side surface of the silicone layer 4 is connected to the first bottom glass 2, and the other side surface faces away from the first cover glass 1; the first cover glass 1 and the first bottom glass 2 are connected by the first adhesive layer 3, and the first adhesive layer 3 surrounds the silicone layer 4; the silicone layer 4 is a silicone film layer; the material of the first adhesive layer 3 is butyl rubber; the thickness of the silicone layer 4 is 527 nm, and the Shore hardness is 7; the thickness of the first adhesive layer 3 is 0.6 mm; the thickness of the first bottom glass 2 is 3 mm, and the thickness of the first cover glass 1 is 3 mm, both of which are non-tempered glass;

[0074] The lamination process conditions include: vacuuming, first-stage pressure holding, second-stage pressure holding, and lamination; the vacuuming time is 400s; the first-stage pressure holding pressure is -80kPa, the first-stage pressure holding time is 300s, the second-stage pressure holding pressure is -60kPa, the second-stage pressure holding time is 600s, the lamination time is 2s, the lamination pressure is 60kPa, and the lamination temperature is 120℃.

[0075] (b) Assemble the perovskite module base layer 7, support frame 9, second adhesive layer 8, second bottom glass 6, and second cover glass 5 to form a second assembly. See the schematic diagram of the main cross-sectional structure of the second assembly. Figure 2 Using the lamination process conditions of step (a), the second assembly is laminated to obtain a perovskite photovoltaic module.

[0076] In the second assembly, the second bottom glass 6 and the second cover glass 5 are arranged face to face; one side surface of the perovskite module base layer 7 is connected to the second bottom glass 6, and the other side surface faces away from and away from the second cover glass 5; the second bottom glass 6 and the second cover glass 5 are connected by the second adhesive layer 8, and the second adhesive layer 8 surrounds the perovskite module base layer 7; the support frame 9 is located between the perovskite module base layer 7 and the second cover glass 5, and the support frame 9 is connected to the perovskite module base layer 7; along the direction from the second bottom glass 6 to the second cover glass 5, the perovskite module base layer 7 sequentially includes a transparent electrode layer, a first charge transport layer, a perovskite film layer (PVSK film), a second charge transport layer, a barrier layer, and a back electrode layer;

[0077] The support frame 9 is dot-shaped, with four dots connected sequentially to form a rectangle, located in the central region of the perovskite module base layer 7; the support frame 9 is made of PTFE; after lamination, the thickness of the support frame 9 is 600μm; the first charge transport layer is NiO. x The thickness is 30 nm; the thickness of the perovskite film is 400 nm; the second charge transport layer is C 60 Layer and SnO2 layer, C 60 The thickness of the layer is 15nm, and the thickness of the SnO2 layer is 5nm; the barrier layer is a BCP layer with a thickness of 60nm; the back electrode layer is a Cu layer with a thickness of 15nm; the transparent electrode layer is an FTO layer with a thickness of 2mm; the thickness of the second adhesive layer 8 is 0.7mm; the second cover glass 5 and the second bottom glass 6 are both non-tempered glass with a thickness of 3mm.

[0078] (c) Conduct an appearance inspection of the laminated perovskite photovoltaic module (sample) to ensure that there is no damage or discoloration in the non-support area after lamination. After confirming that the sample is qualified, transfer the sample to the later testing stage. Before connecting the DC power supply, the sample needs to be tested for power. Then, the sample is DC powered on. The DC power supply specification needs to be determined according to the JV parameters measured on the sample to determine the power supply range. During the power supply process, the light-absorbing surface of the sample needs to be protected from light to prevent the photocurrent and the current current from generating current collision and heating. This power supply process can be carried out at room temperature until the film surface shows white aggregation. Then, stop the power supply, disassemble and cut to obtain the white area on the film surface, complete the sample preparation according to the SEM sample preparation requirements, and then perform SEM detection and analyze the data.

[0079] Example 3

[0080] A general analytical method for identifying whitening of the perovskite photovoltaic module film surface includes the following steps:

[0081] (a) Assemble the silicone layer 4, the first adhesive layer 3, the first bottom glass 2, and the first cover glass 1 to form a first assembly, such as Figure 1 As shown, further lamination adjustments are performed to obtain the lamination process conditions corresponding to the absence of contact between the first cover glass 1 and the silicone layer 4 after lamination.

[0082] In the first assembly, the first cover glass 1 and the first bottom glass 2 are arranged face to face; one side surface of the silicone layer 4 is connected to the first bottom glass 2, and the other side surface faces away from the first cover glass 1; the first cover glass 1 and the first bottom glass 2 are connected by the first adhesive layer 3, and the first adhesive layer 3 surrounds the silicone layer 4; the silicone layer 4 is a silicone film layer; the material of the first adhesive layer 3 is butyl rubber; the thickness of the silicone layer 4 is 647 nm, and the Shore hardness is 18; the thickness of the first adhesive layer 3 is 0.8 mm; the thickness of the first bottom glass 2 is 6 mm, and the thickness of the first cover glass 1 is 6 mm, both of which are non-tempered glass;

[0083] The lamination process conditions include: vacuuming, first-stage pressure holding, second-stage pressure holding, and lamination; the vacuuming time is 400s; the first-stage pressure holding pressure is -80kPa, the first-stage pressure holding time is 300s, the second-stage pressure holding pressure is -60kPa, the second-stage pressure holding time is 600s, the lamination time is 5s, the lamination pressure is 60kPa, and the lamination temperature is 110℃.

[0084] (b) Assembling the perovskite module base layer 7, support frame 9, second adhesive layer 8, second bottom glass 6, and second cover glass 5 to form a second assembly. The main sectional view of the second assembly is shown in the schematic diagram. Figure 2Similar to (the difference being that the support frame 9 is replaced by a grid instead of dots), the second assembly is laminated using the lamination process conditions of step (a) to obtain a perovskite photovoltaic module;

[0085] In the second assembly, the second bottom glass 6 and the second cover glass 5 are arranged face to face; one side surface of the perovskite module base layer 7 is connected to the second bottom glass 6, and the other side surface faces away from and away from the second cover glass 5; the second bottom glass 6 and the second cover glass 5 are connected by the second adhesive layer 8, and the second adhesive layer 8 surrounds the perovskite module base layer 7; the support frame 9 is located between the perovskite module base layer 7 and the second cover glass 5, and the support frame is connected to the perovskite module base layer 7; along the direction from the second bottom glass 6 to the second cover glass 5, the perovskite module base layer 7 sequentially includes a transparent electrode layer, a first charge transport layer, a perovskite film layer (PVSK film), a second charge transport layer, a barrier layer, and a back electrode layer;

[0086] The support frame 9 has a mesh-like shape; the material of the support frame 9 is PIB; after lamination, the thickness of the support frame 9 is 650 μm; the first charge transport layer is NiO. x The thickness is 50 nm; the thickness of the perovskite film is 450 nm; the second charge transport layer is C 60 Layer and SnO2 layer, C 60 The thickness of the layer is 25nm, and the thickness of the SnO2 layer is 15nm; the barrier layer is a BCP layer with a thickness of 80nm; the back electrode layer is a Cu layer with a thickness of 25nm; the transparent electrode layer is an FTO layer with a thickness of 2mm; the thickness of the second adhesive layer 8 is 0.8mm; the second cover glass 5 and the second bottom glass 6 are both non-tempered glass with a thickness of 6mm.

[0087] (c) Conduct an appearance inspection of the laminated perovskite photovoltaic module (sample) to ensure that there is no damage or discoloration in the non-support area after lamination. After confirming that the sample is qualified, transfer the sample to the later testing stage. Before connecting the DC power supply, the sample needs to be tested for power. Then, the sample is DC powered on. The DC power supply specification needs to be determined according to the JV parameters measured on the sample to determine the power supply range. During the power supply process, the light-absorbing surface of the sample needs to be protected from light to prevent the photocurrent and the current current from generating current collision and heating. This power supply process can be carried out at room temperature until the film surface shows white aggregation. Then, stop the power supply, disassemble and cut to obtain the white area on the film surface, complete the sample preparation according to the SEM sample preparation requirements, and then perform SEM detection and analyze the data.

[0088] Test case

[0089] In Embodiment 1 of this invention, after the perovskite module undergoes a TC power-on aging test according to the IEC61215 aging sequence test requirements, the light-absorbing surface of the module changes from a uniform dark brown film to a non-uniform white film. (See [link to previous section]). Figure 4 As shown.

[0090] The whitish film surface in Example 1 was examined using a scanning electron microscope (SEM). See [link to SEM image]. Figure 5 , Figure 5 (a1) is a surface SEM image of the perovskite in the sampled whitish area. As can be seen from the image, there are many white particles on the perovskite film surface. Figure 5 (a2) is a SEM image of the underside of the perovskite in the whitish region, where many pores appear. Figure 5 Image (a3) ​​is a SEM image of the cross-section of the white perovskite, which better shows the overall degradation of the white perovskite. The image shows that the perovskite has pores throughout, which leads to the degradation of device performance.

[0091] This invention provides a universal analytical method for identifying whitening on the surface of perovskite photovoltaic modules. The sampling method is simple and can restore the whitening phenomenon of perovskite modules without damage. It is easy to operate and has very low equipment requirements. It can analyze the causes of whitening on the surface of perovskite photovoltaic modules more accurately and intuitively, and is highly efficient.

[0092] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A universal analytical method for identifying whitening of the perovskite photovoltaic module film surface, characterized in that, Includes the following steps: (a) The first assembly formed by the silicone layer, the first adhesive layer, the first bottom glass and the first cover glass is laminated and tested to obtain the lamination process conditions corresponding to the first cover glass and the silicone layer having no contact after lamination. (b) Using the lamination process conditions of step (a), the second assembly formed by the perovskite module base layer, support frame, second adhesive layer, second bottom glass and second cover glass is laminated to obtain a perovskite photovoltaic module; (c) After confirming that the perovskite photovoltaic module is qualified, an aging process is performed until the perovskite photovoltaic module shows white film on the surface. The white film area is then obtained and detected and analyzed.

2. The general analytical method for identifying whitening of perovskite photovoltaic module film surface according to claim 1, characterized in that, It includes at least one of the following features (1) to (3): (1) The silica-containing layer includes at least one of a silica film layer and a polydimethylsiloxane film layer; (2) The Shore hardness of the silicone layer is 5 to 20 degrees; (3) The thickness of the silicone layer is ≤5μm.

3. The general analytical method for identifying whitening of perovskite photovoltaic module film surface according to claim 1, characterized in that, In the first assembly, the first cover glass and the first bottom glass are arranged face to face; one side surface of the silicone layer is connected to the first bottom glass, and the other side surface faces away from the first cover glass; the first cover glass and the first bottom glass are connected by the first adhesive layer, and the first adhesive layer surrounds the silicone layer.

4. The general analytical method for identifying whitening of perovskite photovoltaic module film surface according to claim 3, characterized in that, It includes at least one of the following features (1) to (2): (1) The thickness of the first adhesive layer is 0.5 to 0.9 mm; (2) Both the first cover glass and the first bottom glass are non-tempered glass with a thickness of 2.2 to 10 mm.

5. The general analytical method for identifying whitening of perovskite photovoltaic module film surface according to claim 1, characterized in that, The lamination process conditions in step (a) include: vacuuming, first-stage pressure holding, second-stage pressure holding, and lamination.

6. The general analytical method for identifying whitening of the perovskite photovoltaic module film surface according to claim 1, characterized in that, It includes at least one of the following features (1) to (4): (1) In the second assembly, the second bottom glass and the second cover glass are arranged face to face; one side surface of the perovskite module base layer is connected to the second bottom glass, and the other side surface faces away from and away from the second cover glass; the second bottom glass and the second cover glass are connected by the second adhesive layer, and the second adhesive layer surrounds the perovskite module base layer; the support frame is located between the perovskite module base layer and the second cover glass, and the support frame is connected to the perovskite module base layer; (2) Along the direction from the second bottom glass to the second cover glass, the perovskite module base layer sequentially includes a transparent electrode layer, a first charge transport layer, a perovskite film layer, a second charge transport layer and a back electrode layer; (3) The perovskite module base layer also includes a barrier layer; (4) The thickness of the second adhesive layer is 0.5 to 0.9 mm.

7. The general analytical method for identifying whitening of perovskite photovoltaic module film surface according to claim 1 or 5, characterized in that, It includes at least one of the following features (1) to (3): (1) The shape of the support frame includes at least one of dot-shaped, line-shaped and grid-shaped; (2) The material of the support frame includes at least one of POE, PVB, PIB and PTFE; (3) In the perovskite photovoltaic module, the thickness of the support frame is 200-1000μm.

8. The general analytical method for identifying whitening of the perovskite photovoltaic module film surface according to any one of claims 1 to 6, characterized in that, The first cover glass and the second cover glass are made of the same material and have the same thickness; The first and second bottom glass panels are made of the same material and have the same thickness; The first adhesive layer and the second adhesive layer are made of the same material and have the same thickness; The silicone-containing layer has the same thickness as the perovskite module base layer.

9. The general analytical method for identifying whitening of the perovskite photovoltaic module film surface according to any one of claims 1 to 6, characterized in that, The aging process includes electrical aging. Before power-on aging, the qualified perovskite photovoltaic modules are subjected to power testing.

10. The general analytical method for identifying whitening of the perovskite photovoltaic module film surface according to any one of claims 1 to 6, characterized in that, In step (c), the whitened area of ​​the perovskite photovoltaic module is obtained by disassembling and cutting the whitened area of ​​the film surface; the whitened area of ​​the film surface is then subjected to SEM detection and analysis.

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