Four-terminal perovskite crystal silicon laminated battery assembly and preparation method thereof

Abstract

The invention belongs to the photovoltaic field, and particularly relates to a four-terminal perovskite crystalline silicon laminated battery assembly and a preparation method thereof. The four-end perovskite crystalline silicon laminated cell assembly sequentially comprises a front cover plate, an adhesive film a, a perovskite cell, transparent metal oxide glass, an adhesive film b, a crystalline silicon cell, an adhesive film c and a rear cover plate, the adhesive film a is a non-crosslinked polyolefin elastomer adhesive film; the adhesive film b is made of a cross-linked polyolefin elastomer and / or a cross-linked polyethylene-polyvinyl acetate copolymer; and the adhesive film c is made of a cross-linked polyolefin elastomer and / or a cross-linked polyethylene-polyvinyl acetate copolymer. The reliability and the preparation flexibility of the four-end perovskite crystalline silicon laminated battery assembly comprising the barrier layer composed of the transparent metal oxide glass and the adhesive film which is specifically arranged, combined and distributed are improved.

Description

Technical Field

[0001] The present invention belongs to the field of photovoltaics, and in particular relates to a four-terminal perovskite crystalline silicon stacked cell assembly and a preparation method thereof. Background Art

[0002] In existing photovoltaic technology, a four-terminal perovskite crystalline silicon tandem cell module consists of a stacked structure consisting of a glass layer, a perovskite cell, an adhesive film, a crystalline silicon cell, an adhesive film, and a glass layer. Similar four-terminal tandem structures based on this stacked structure can also be improved. The four-terminal perovskite crystalline silicon tandem cell module improves spectral utilization through a wide-bandgap and narrow-bandgap combination, reducing out-of-band absorption and thermal relaxation in crystalline silicon cells, thereby reducing costs and increasing efficiency.

[0003] However, on the one hand, due to the sensitivity of perovskite materials to light, heat, water and oxygen, especially the instability of perovskite materials under ultraviolet light and easy decomposition at high temperatures, how to ensure the stability of the battery components after packaging is still a problem. Conventional crystalline silicon battery packaging process can achieve water and oxygen barrier, but the lamination temperature of conventional crystalline silicon battery packaging is 140-160℃, and heat-crosslinked EVA film is used. Although this packaging condition can reduce the risk of crystalline silicon battery cells being paralleled due to film creep during outdoor use, perovskite batteries are not resistant to high temperatures. At high temperatures (greater than 140℃), there may be risks such as phase change, decomposition, and interfacial reaction. The lamination temperature of perovskite batteries needs to be less than 120℃, but at this temperature, the film cannot be thermally cross-linked, resulting in risks to the reliability of crystalline silicon batteries. Therefore, the packaging process of conventional crystalline silicon batteries cannot be completely replicated for the packaging of four-terminal perovskite crystalline silicon stacked battery components.

[0004] On the other hand, the traditional four-terminal perovskite crystalline silicon stacked cell module uses a film to stick the perovskite cell and the crystalline silicon cell together. During processing, the stacked components of this structure can only be fully stacked and laid out at one time and packaged using a single lamination process. There are problems such as long production process, large single investment, incompatibility of process parameters of perovskite cells and crystalline silicon cells under single lamination, and poor flexibility in the entire production process.

[0005] Therefore, there is an urgent need to develop a four-terminal perovskite crystalline silicon stacked battery component with high reliability and flexible preparation process. Summary of the Invention

[0006] To address the problems of the prior art, the present invention provides a four-terminal perovskite crystalline silicon tandem cell assembly. The four-terminal perovskite crystalline silicon tandem cell assembly comprises, in order, a front cover, a film a, a perovskite cell, a transparent metal oxide glass, a film b, a crystalline silicon cell, a film c, and a rear cover. Film a is a non-crosslinked polyolefin elastomer (POE) film, film b is made of crosslinked POE or crosslinked polyethylene-polyvinyl acetate copolymer (EVA), and film c is made of crosslinked POE or crosslinked EVA. The transparent metal oxide glass and the film arranged in a specific combination and distribution can effectively improve the reliability and production flexibility of the four-terminal perovskite crystalline silicon tandem cell assembly.

[0007] Specifically, the present invention provides a four-terminal perovskite crystalline silicon stacked cell assembly, which comprises a front cover, a film a, a perovskite cell, a transparent metal oxide glass, a film b, a crystalline silicon cell, a film c and a back cover in sequence; the film a is a non-cross-linked polyolefin elastomer; the material of the film b is a cross-linked polyolefin elastomer and / or a cross-linked polyethylene-polyvinyl acetate copolymer; the material of the film c is a cross-linked polyolefin elastomer and / or a cross-linked polyethylene-polyvinyl acetate copolymer; the cross-linked polyolefin elastomer is cross-linked by a cross-linkable polyolefin elastomer and a cross-linking agent; the cross-linked polyethylene-polyvinyl acetate copolymer is cross-linked by a cross-linkable polyethylene-polyvinyl acetate copolymer and a cross-linking agent.

[0008] In one or more embodiments, the thickness of the adhesive film a is 0.1-1 mm.

[0009] In one or more embodiments, the transparent metal oxide glass has a thickness of 0.2-3.2 mm.

[0010] In one or more embodiments, the thickness of the adhesive film b is 0.1-1 mm.

[0011] In one or more embodiments, the thickness of the adhesive film c is 0.1-1 mm.

[0012] In one or more embodiments, the cross-linkable polyolefin elastomer is a polyolefin elastomer that can be cross-linked by ultraviolet radiation or a polyolefin elastomer that can be cross-linked by heat.

[0013] In one or more embodiments, the cross-linkable polyethylene-polyvinyl acetate copolymer is a polyethylene-polyvinyl acetate copolymer that can be cross-linked by ultraviolet radiation or a polyethylene-polyvinyl acetate copolymer that can be cross-linked by heat.

[0014] In one or more embodiments, the crosslinking agent is a thermal crosslinking agent or an ultraviolet radiation crosslinking agent.

[0015] In one or more embodiments, the thermal crosslinking agent is a peroxide, preferably di-tert-butyl peroxide and / or dicumyl peroxide.

[0016] In one or more embodiments, the ultraviolet radiation crosslinking agent is a benzophenone photoinitiator and / or an inorganic powder composite photoinitiator, preferably selected from one or more of benzophenone, 4-lauroyloxydibenzoyl ketone, antimony-doped tin oxide and rutile titanium dioxide.

[0017] In one or more embodiments, the transparent metal oxide glass is indium tin oxide glass or fluorine-doped tin oxide glass.

[0018] In one or more embodiments, the four-terminal perovskite crystalline silicon stacked cell assembly further includes a packaging component; the packaging component is located between the transparent metal oxide glass and the front cover; and the packaging component is an annular structure.

[0019] In one or more embodiments, the packaging component is made of butyl rubber.

[0020] The method for preparing a four-terminal perovskite crystalline silicon stacked battery assembly provided by the present invention comprises the following steps:

[0021] (1) stacking a front cover plate, a film a precursor, a perovskite cell, and a transparent metal oxide glass in sequence from top to bottom, and then laminating to obtain a perovskite component;

[0022] (2) stacking the perovskite component, the adhesive film b precursor, the crystalline silicon cell, the adhesive film c precursor and the back cover in order from top to bottom, and then laminating them, and finally irradiating them with ultraviolet light from the back cover to obtain a four-terminal perovskite crystalline silicon stacked cell component; or

[0023] (1') stacking transparent metal oxide glass, adhesive film b precursor, crystalline silicon cell, adhesive film c precursor and rear cover plate in order from top to bottom, and then laminating to obtain a crystalline silicon module;

[0024] (2') Growing a perovskite cell on the transparent metal oxide glass of the crystalline silicon component to obtain an intermediate, stacking a front cover plate, a film a precursor and the intermediate in sequence from top to bottom, and then laminating to obtain a four-terminal perovskite crystalline silicon stacked cell component.

[0025] In one or more embodiments, the film a precursor is converted into film a; the film b precursor is converted into film b; and the film c precursor is converted into film c.

[0026] In one or more embodiments, the film a precursor is a non-crosslinked polyolefin elastomer.

[0027] In one or more embodiments, the adhesive film b precursor comprises a cross-linkable polyolefin elastomer and / or a cross-linkable polyethylene-polyvinyl acetate copolymer;

[0028] In one or more embodiments, the adhesive film c precursor comprises a cross-linkable polyolefin elastomer and / or a cross-linkable polyethylene-polyvinyl acetate copolymer.

[0029] In one or more embodiments, in step (1), the lamination temperature is 90-120°C.

[0030] In one or more embodiments, in step (2), the lamination temperature is 90-120°C.

[0031] In one or more embodiments, in step (1'), the lamination temperature is 140-160°C.

[0032] In one or more embodiments, in step (2'), the lamination temperature is 90-120°C.

[0033] In one or more embodiments, in step (2), the adhesive film b precursor further comprises an ultraviolet light irradiation crosslinking agent.

[0034] In one or more embodiments, in step (2), the adhesive film c precursor further comprises an ultraviolet light irradiation crosslinking agent.

[0035] In one or more embodiments, in step (2), the cross-linkable polyolefin elastomer is a polyolefin elastomer that can be cross-linked by ultraviolet light.

[0036] In one or more embodiments, in step (2), the cross-linkable polyethylene-polyvinyl acetate copolymer is a polyethylene-polyvinyl acetate copolymer that can be cross-linked by ultraviolet light.

[0037] In one or more embodiments, in step (1'), the adhesive film b precursor further comprises a thermal crosslinking agent or an ultraviolet radiation crosslinking agent.

[0038] In one or more embodiments, in step (1'), the adhesive film c precursor further comprises a thermal crosslinking agent.

[0039] In one or more embodiments, in step (1'), the cross-linkable polyolefin elastomer is a polyolefin elastomer that can be cross-linked by ultraviolet radiation or a polyolefin elastomer that can be cross-linked by heat.

[0040] In one or more embodiments, in step (1'), the cross-linkable polyethylene-polyvinyl acetate copolymer is a polyethylene-polyvinyl acetate copolymer that can be cross-linked by ultraviolet radiation or a polyethylene-polyvinyl acetate copolymer that can be cross-linked by heat.

[0041] In one or more embodiments, in step (1'), in step (1'), the film b precursor contains a thermal crosslinking agent, the film c precursor contains a thermal crosslinking agent, the crosslinkable polyolefin elastomer is a thermally crosslinkable polyolefin elastomer, and the crosslinkable polyethylene-polyvinyl acetate copolymer is a thermally crosslinkable polyethylene-polyvinyl acetate copolymer. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 Schematic diagram of the structure of the perovskite component of some embodiments of the present invention, wherein 0 is the packaging component, 1 is the front cover, 2 is the adhesive film a, 3 is the perovskite cell, and 4 is the transparent metal oxide glass.

[0043] Figure 2 Schematic diagram of the structure of crystalline silicon components according to some embodiments of the present invention, wherein 4 is transparent metal oxide glass, 5 is adhesive film b, 6 is crystalline silicon cell, 7 is adhesive film c, and 8 is rear cover.

[0044] Figure 3 This is a schematic structural diagram of a four-terminal perovskite crystalline silicon stacked cell assembly according to some embodiments of the present invention, wherein 0 is a packaging component, 1 is a front cover, 2 is a film a, 3 is a perovskite cell, 4 is a transparent metal oxide glass, 5 is a film b, 6 is a crystalline silicon cell, 7 is a film c, and 8 is a rear cover.

[0045] Figure 4 A process flow chart for preparing four-terminal perovskite crystalline silicon stacked battery components according to some embodiments of the present invention. DETAILED DESCRIPTION

[0046] To facilitate understanding of the features and effects of the present invention by those skilled in the art, the following provides a general description and definition of the terms and expressions used in the specification and claims. Unless otherwise indicated, all technical and scientific terms used herein have the ordinary meanings as understood by those skilled in the art regarding the present invention. In the event of conflict, the definitions in this specification shall prevail.

[0047] The theories or mechanisms described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, that is, the present invention can be implemented without being limited by any specific theory or mechanism.

[0048] Herein, “comprising,” “including,” “containing” and similar terms encompass the meanings of “consisting essentially of” and “consisting of,” for example, when “A comprises B and C” is disclosed herein, “A consists essentially of B and C” and “A consists of B and C” should be deemed to have been disclosed herein.

[0049] Throughout this document, all features, such as values, amounts, amounts, and concentrations, specified in numerical ranges or percentage ranges are provided for simplicity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to encompass and specifically disclose all possible subranges and individual values ​​within those ranges (including integers and fractions).

[0050] In this document, unless otherwise specified, percentage refers to mass percentage and ratio refers to mass ratio.

[0051] Herein, when describing embodiments or examples, it should be understood that they are not intended to limit the present invention to these embodiments or examples. On the contrary, all alternatives, modifications and equivalents of the methods and materials described herein are encompassed within the scope defined by the claims.

[0052] In this document, for the sake of brevity, not all possible combinations of the various technical features in each embodiment or example are described. Therefore, as long as there are no contradictions in the combination of these technical features, the various technical features in each embodiment or example can be combined in any way, and all possible combinations should be considered to be within the scope of this specification.

[0053] The four-terminal perovskite crystalline silicon stacked cell assembly of the present invention may sequentially comprise a front cover, a film a, a perovskite cell, a transparent metal oxide glass, a film b, a crystalline silicon cell, a film c and a back cover. The specific structure is as follows: Figure 3 As shown. In the present invention, the film a can be a non-cross-linked POE film. In some embodiments, the film a has an ultraviolet light conversion function. In the present invention, the material of the film b can be a cross-linked polyolefin elastomer and / or a cross-linked polyethylene-polyvinyl acetate copolymer. In the present invention, the material of the film c can be a cross-linked polyolefin elastomer and / or a cross-linked polyethylene-polyvinyl acetate copolymer. In the present invention, by setting the specific materials and relative positions of the film a, film b, film c and transparent metal oxide glass, the efficiency, high temperature performance, aging performance and insulation performance of the four-terminal perovskite crystalline silicon stacked battery component can be effectively guaranteed through synergistic effect, that is, the reliability of the four-terminal perovskite crystalline silicon stacked battery component is improved. Setting the film a with ultraviolet cutoff or light conversion function can more effectively synergize with the film b and film c to improve the reliability of the four-terminal perovskite crystalline silicon stacked battery component.

[0054] In the present invention, the crosslinked polyolefin elastomer is formed by crosslinking a crosslinkable polyolefin elastomer and a crosslinking agent; in the present invention, the crosslinked polyethylene-polyvinyl acetate copolymer is formed by crosslinking a crosslinkable polyethylene-polyvinyl acetate copolymer and a crosslinking agent. In the present invention, the crosslinkable polyolefin elastomer can be a polyolefin elastomer crosslinkable by ultraviolet radiation or a polyolefin elastomer crosslinkable by heat. In the present invention, the crosslinkable polyethylene-polyvinyl acetate copolymer can be a polyethylene-polyvinyl acetate copolymer crosslinkable by ultraviolet radiation or a polyethylene-polyvinyl acetate copolymer crosslinkable by heat. In the present invention, the crosslinking agent is a thermal crosslinking agent or an ultraviolet radiation crosslinking agent; in the present invention, the thermal crosslinking agent can be a peroxide, preferably di-tert-butyl peroxide (DTBP) and / or diisopropylbenzene peroxide (DCP); in the present invention, the ultraviolet radiation crosslinking agent can be a benzophenone photoinitiator and / or an inorganic powder composite photoinitiator, preferably selected from one or more of benzophenone (BP), 4-lauroyloxydimethylbenzene, antimony-doped tin oxide (ATO), and rutile titanium dioxide (TiO2). In the present invention, the use of the specific materials of the above-mentioned adhesive films a, b, and c can effectively ensure the efficiency, high-temperature performance, aging performance, and insulation performance of the four-terminal perovskite crystalline silicon tandem battery module.

[0055] In the present invention, the transparent metal oxide glass may be indium tin oxide glass or fluorine-doped tin oxide (FTO) glass. In the present invention, the provision of the transparent metal oxide glass can effectively enhance the flexibility of preparing the four-terminal perovskite crystalline silicon stacked cell assembly.

[0056] In the present invention, the thickness of the adhesive film a can be 0.1-1 mm, for example, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, or 1 mm. In the present invention, the thickness of the transparent metal oxide glass can be 0.2-3.2 mm, for example, 0.2 mm, 0.6 mm, 1.0 mm, 1.4 mm, 1.8 mm, 2.2 mm, 2.6 mm, or 3.0 mm. In the present invention, the thickness of the adhesive film b can be 0.1-1 mm, for example, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, or 1 mm. In the present invention, the thickness of the adhesive film c can be 0.1-1 mm, for example, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, or 1 mm.

[0057] In the present invention, the front cover is tempered glass. In the present invention, the thickness of the front cover can be 0.1-3.0 mm, for example, 0.5 mm, 1.0 mm, 1.5 mm, 2.0 mm, 2.5 mm, or 3 mm. In the present invention, the rear cover can be tempered glass. In the present invention, the four-terminal perovskite crystalline silicon tandem cell assembly can further include an encapsulation component; the encapsulation component can be located between the transparent metal oxide glass and the front cover; the encapsulation component can have an annular structure. The encapsulation component of the present invention is made of butyl rubber.

[0058] The present invention provides a method for preparing a four-terminal perovskite crystalline silicon stacked battery component, the method comprising the following steps:

[0059] (1) A front cover plate, a film precursor, a perovskite cell, and a transparent metal oxide glass are stacked in sequence from top to bottom, and then laminated to obtain a perovskite component (such as Figure 1 As shown); wherein, the film a precursor is converted into film a;

[0060] (2) stacking a perovskite component, a film b precursor, a crystalline silicon cell, a film c precursor, and a back cover in sequence from top to bottom, laminating the components, and finally irradiating the components with ultraviolet light from the back cover to obtain a four-terminal perovskite crystalline silicon stacked cell component; wherein the film b precursor is converted into film b, and the film c precursor is converted into film c; or

[0061] (1') Transparent metal oxide glass, adhesive film b precursor, crystalline silicon cell, adhesive film c precursor and rear cover are stacked in order from top to bottom, and then laminated to obtain a crystalline silicon module (such as Figure 2 As shown); wherein, the film b precursor is converted into film b, and the film c precursor is converted into film c;

[0062] (2') growing a perovskite cell on the transparent metal oxide glass of a crystalline silicon module to obtain an intermediate, stacking a front cover plate, a film a precursor, and the intermediate in sequence from top to bottom, and then laminating to obtain a four-terminal perovskite crystalline silicon stacked cell module; wherein the film a precursor is converted into film a.

[0063] The preparation method of the present invention can solve a series of reliability problems existing in four-terminal perovskite crystalline silicon stacked battery components, such as perovskite battery efficiency attenuation, perovskite material degradation, crystalline silicon battery cell displacement and paralleling, and short circuit between perovskite and crystalline silicon circuits. It also optimizes the component structure and production route, shortens the time of single production, and improves production flexibility.

[0064] In the present invention, the precursor of Film A can be a non-crosslinked POE. In the present invention, the precursor of Film B comprises a crosslinkable polyolefin elastomer and / or a crosslinkable polyethylene-polyvinyl acetate copolymer. In the present invention, the precursor of Film C can comprise a crosslinkable polyolefin elastomer and / or a crosslinkable polyethylene-polyvinyl acetate copolymer. The precursors of Film A, Film B, and Film C of the present invention are converted into Film A, Film B, and Film C, respectively, after lamination.

[0065] In step (2), the film b precursor may further comprise an ultraviolet light crosslinking agent. In step (2), the film c precursor may further comprise an ultraviolet light crosslinking agent. In step (2), the crosslinkable polyolefin elastomer may be an ultraviolet light crosslinkable polyolefin elastomer. In step (2), the crosslinkable polyethylene-polyvinyl acetate copolymer may be an ultraviolet light crosslinkable polyethylene-polyvinyl acetate copolymer. In some embodiments, the film b precursor is an ultraviolet light crosslinkable polyolefin elastomer and an ultraviolet light crosslinking agent. In some embodiments, the film c precursor is an ultraviolet light crosslinkable polyolefin elastomer and an ultraviolet light crosslinking agent. In some embodiments, the film b precursor is an ultraviolet light crosslinkable polyethylene-polyvinyl acetate copolymer and an ultraviolet light crosslinking agent. In some embodiments, the film c precursor is an ultraviolet light crosslinkable polyethylene-polyvinyl acetate copolymer and an ultraviolet light crosslinking agent.

[0066] In step (1'), the film b precursor may further comprise a thermal crosslinker or an ultraviolet irradiation crosslinker, preferably a thermal crosslinker. In step (1'), the film c precursor may further comprise a thermal crosslinker. In step (1'), the crosslinkable polyolefin elastomer is a polyolefin elastomer that can be crosslinked by ultraviolet irradiation or a thermal crosslinkable polyolefin elastomer, preferably a thermal crosslinkable polyolefin elastomer. In step (1'), the crosslinkable polyethylene-polyvinyl acetate copolymer may be a polyethylene-polyvinyl acetate copolymer that can be crosslinked by ultraviolet irradiation or a thermal crosslinkable polyethylene-polyvinyl acetate copolymer, preferably a thermal crosslinkable polyethylene-polyvinyl acetate copolymer. In some embodiments, the film b precursor is a thermal crosslinkable polyolefin elastomer and a thermal crosslinker. In some embodiments, the film c precursor is a thermal crosslinkable polyolefin elastomer and a thermal crosslinker. In some embodiments, the film b precursor is a thermal crosslinkable polyethylene-polyvinyl acetate copolymer and a thermal crosslinker. In some embodiments, the adhesive film c precursor is a thermally cross-linkable polyethylene-polyvinyl acetate copolymer and a thermal cross-linking agent.

[0067] In step (1), the lamination temperature may be 90-120° C., for example, 90° C., 95° C., 100° C., 105° C., 110° C., 115° C., and 120° C. In step (2), the lamination temperature may be 90-120° C., for example, 90° C., 95° C., 100° C., 105° C., 110° C., 115° C., and 120° C.

[0068] In step (1'), the lamination temperature may be 140-160°C, for example, 140°C, 145°C, 150°C, 155°C, 160°C. In step (2'), the lamination temperature may be 90-120°C, for example, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C.

[0069] Compared with the prior art, the present invention has the following beneficial technical effects:

[0070] (1) The packaging structure of the present invention can improve the reliability of the four-terminal perovskite crystalline silicon stacked cell assembly, avoid the efficiency attenuation of the perovskite cell in the package and the degradation in actual operation, and avoid the displacement and paralleling problem of the crystalline silicon cell slices, as well as the possible short circuit problem between the perovskite and crystalline silicon circuits;

[0071] (2) The structure of the present invention can be realized through a new processing method, which solves the problem that the traditional laminated component can only complete the production of the entire laminated component at one time under a complete set of processes; the designed laminated component structure can be divided into different processes, and the perovskite component and the crystalline silicon component can be independently produced, and then further processed into a four-terminal laminated component; the processing of the independent perovskite component and the crystalline silicon component provides a wider optimization space for the production and lamination process, and can be more adaptable to the corresponding components; this processing method improves the flexibility of production, and production is no longer restricted by time and space. Each processing process can be completed at different times and places, providing more options for the optimization and upgrading of the final laminated component product.

[0072] The present invention will be described below by way of specific examples. It should be understood that these examples are merely illustrative and are not intended to limit the scope of the present invention. The methods, reagents, and materials used in the examples are, unless otherwise stated, conventional methods, reagents, and materials in the art. The starting compounds in the examples can all be purchased from commercial sources.

[0073] The UV-crosslinkable EVA material in the examples and comparative examples of the present invention was purchased from Dow Chemical Company of the United States and has the brand name Elvax 40L-03.

[0074] The heat-crosslinkable EVA material in the examples and comparative examples of the present invention was purchased from Parkson Technology, with the brand name MS-M-0190.

[0075] The non-crosslinked POE material with UV cutoff function in the examples and comparative examples of the present invention was purchased from Dow Chemical Company of the United States under the brand name ENGAGE TM PV 8669.

[0076] The non-crosslinked POE material without UV cutoff function in the comparative example of the present invention was purchased from Dow Chemical Company of the United States under the brand name ENGAGE TM PV 8669.

[0077] Example 1

[0078] Preparation of this example Figure 3 The four-terminal perovskite crystalline silicon stacked cell assembly shown in the figure has the following specific steps:

[0079] (1) A 1.6 mm tempered glass front cover, a 0.5 mm adhesive film a (non-crosslinked POE adhesive film with UV cutoff function), a perovskite cell, and a 2.0 mm FTO glass were stacked in sequence from top to bottom, and then laminated at a temperature of 120 ° C to obtain a perovskite component (such as Figure 1 wherein the film a precursor is converted into a film a having a thickness of 0.35 mm;

[0080] (2) A perovskite component, a 0.5 mm adhesive film b precursor, a crystalline silicon cell, a 0.5 mm adhesive film c precursor, and a 1.6 mm tempered glass back cover are stacked in sequence from top to bottom, laminated at a temperature of 120°C, and then irradiated with ultraviolet light from the back cover toward the inside of the cell for 1 minute to completely crosslink the adhesive film c, thereby obtaining a four-terminal perovskite crystalline silicon stacked cell component; wherein the adhesive film b precursor and the adhesive film c precursor are both composed of an ultraviolet-crosslinkable EVA material and 4-lauroyloxydiphenyl ketone in a mass ratio of 1:0.01. After lamination, the adhesive film b precursor and the adhesive film c precursor are converted into an adhesive film b (UV-crosslinkable EVA film) with a thickness of 0.35 mm and an adhesive film c (UV-crosslinkable EVA film) with a thickness of 0.35 mm, respectively.

[0081] Example 2

[0082] Preparation of this example Figure 3 The four-terminal perovskite crystalline silicon stacked cell assembly shown in the figure has the following specific steps:

[0083] (1) 2.0 mm FTO glass, 0.5 mm adhesive film b precursor, crystalline silicon cell, 0.5 mm adhesive film c precursor and 1.6 mm tempered glass back cover are stacked in order from top to bottom and laminated at a temperature of 160 ° C to obtain a crystalline silicon module (such as Figure 2As shown); wherein, the film b precursor and the film c precursor are both composed of a heat-crosslinkable EVA material and dicumyl peroxide in a mass ratio of 1:0.01, and after lamination, the film b precursor and the film c precursor are respectively converted into a film b (heat-crosslinkable EVA film) with a thickness of 0.35 mm and a film c (heat-crosslinkable EVA film) with a thickness of 0.35 mm;

[0084] (2) A perovskite cell is grown on a crystalline silicon component to obtain an intermediate, and a 1.6 mm tempered glass front cover, a 0.5 mm adhesive film a (non-cross-linked POE adhesive film with UV cutoff function) and the intermediate are stacked in sequence from top to bottom, and laminated at a temperature of 120°C to obtain a four-terminal perovskite crystalline silicon stacked cell component, wherein the adhesive film a precursor is converted into an adhesive film a with a thickness of 0.35 mm;

[0085] Comparative Example 1

[0086] In this comparative example, a traditional four-terminal perovskite crystalline silicon stacked cell assembly is prepared, and the specific steps are as follows: 2.0mm FTO glass, perovskite cell, 0.5mm film 1 precursor, crystalline silicon cell, 0.5mm film 2 precursor and 1.6mm tempered glass back cover are stacked in sequence from top to bottom, and laminated at a temperature of 160°C to obtain a traditional four-terminal perovskite crystalline silicon stacked cell assembly; wherein, the film 1 precursor and the film 2 precursor are both composed of heat-crosslinked EVA film and diisopropylbenzene peroxide, and the film b precursor and the film c precursor are converted into a film b (heat-crosslinkable EVA film) with a thickness of 0.35mm and a film c (heat-crosslinkable EVA film) with a thickness of 0.35mm after lamination.

[0087] Comparative Example 2

[0088] Other conditions of this comparative example are the same as those of Example 1, except that in this comparative example, the film b precursor and the film c precursor are replaced with heat-crosslinkable EVA material and dicumyl peroxide, and the lamination temperature is replaced from 120°C to 160°C.

[0089] Comparative Example 3

[0090] Other conditions of this comparative example are the same as those of Example 1, except that the UV-crosslinkable EVA films of films b and c are replaced with non-crosslinked POE films in this comparative example.

[0091] Comparative Example 4

[0092] The other conditions of this comparative example are the same as those of Example 2, except that the adhesive film a in this comparative example is a non-cross-linked POE material without UV cutoff function.

[0093] Test Case

[0094] Performance test of four-terminal perovskite crystalline silicon stacked cell module: at 25°C and AM 1.5G standard solar spectrum, using a solar simulator, setting the voltage range to 0-100V, testing the current output of the four-terminal perovskite crystalline silicon stacked cell modules prepared in Examples 1-2 and Comparative Examples 1-4 before packaging, the four-terminal perovskite crystalline silicon stacked cell modules prepared in Examples 1-2 and Comparative Examples 1-4 after packaging (initial), and the four-terminal perovskite crystalline silicon stacked cell modules prepared in Examples 1-2 and Comparative Examples 1-4 after UV aging at different voltages, and plotting the corresponding current-voltage (IV) characteristic curves, wherein the incident light power (Pin) is 1000W / m 2 According to the characteristic curve, the open circuit voltage, short circuit current density, fill factor and photoelectric conversion efficiency of the corresponding four-terminal perovskite crystalline silicon stacked cell module are obtained. The test results are shown in Tables 1 and 2.

[0095] (1) Open circuit voltage (Voc): The voltage value corresponding to the current being zero.

[0096] (2) Short-circuit current density (Jsc): The current value when the voltage is zero is the short-circuit current (Isc), and the current per unit battery surface area is the short-circuit current density.

[0097] (3) Fill factor (FF): The ratio of the maximum output power (Pmax) of the battery to the product of the open circuit voltage and the short circuit current. The calculation formula is (Pmax / Voc*Isc), where the maximum power point is the point where the battery output power reaches its maximum value.

[0098] (4) Photoelectric conversion efficiency (PCE): Photoelectric conversion efficiency refers to the ratio of maximum output power to incident light power (Pin), and the calculation formula is (Pmax / Pin)*100%.

[0099] The test results of the open circuit voltage, short circuit current density, fill factor and photoelectric conversion efficiency of the four-terminal perovskite crystalline silicon stacked cell components prepared in Examples 1-2 and Comparative Examples 1-4 are shown in Table 1.

[0100] UV15 aging: The four-terminal perovskite crystalline silicon stacked cell components prepared in Examples 1-2 and Comparative Examples 1-4 were placed in an ultraviolet aging test chamber, ensuring that their surfaces were facing the ultraviolet light source. The ultraviolet light source was turned on, and the irradiation intensity and cumulative irradiation amount (15 kWh) were set to obtain the four-terminal perovskite crystalline silicon stacked cell components prepared in Examples 1-2 and Comparative Examples 1-4 after UV aging.

[0101] Insulation withstand voltage test: Use a high-voltage tester to ensure that its output voltage range and accuracy comply with the IEC 61215 standard. Place the four-terminal perovskite crystalline silicon stacked cell module on the insulation test bench, ensure that its surface is dry and free of pollution, and heat it to maintain the module temperature at 85°C. Connect the positive pole of the high-voltage tester to the metal frame of the module, and the negative pole to the output terminal of the module; gradually increase the voltage to the standard value (1000V + 2 times the maximum system voltage of the module) and maintain it for 1 minute; then connect the positive pole of the high-voltage tester to the output terminal of the perovskite module, and the negative pole to the output terminal of the crystalline silicon module; gradually increase the voltage to the standard value (1000V + 2 times the maximum system voltage of the module) and maintain it for 1 minute, and record the test voltage, leakage current, and whether the module has breakdown or leakage, as well as the insulation resistance. Qualification requirements: No insulation breakdown or surface cracks. For an area less than 0.1m 2 The insulation resistance of the components is not less than 400MΩ, and for areas larger than 0.1m 2 For components, the test insulation resistance multiplied by the component area should be no less than 40MΩ·m 2 .

[0102] 120°C thermal bake test: Use a high-temperature test chamber with a temperature control accuracy of ±2°C. Place the four-terminal perovskite crystalline silicon tandem solar cell module in the test chamber, ensuring that its surface is unobstructed. Gradually increase the chamber temperature to 120°C and maintain it stable. Bake the module at 120°C for 24 hours. Close the test chamber, wait for the module to cool to room temperature, remove it, and perform a visual inspection. Acceptance requirements: The module must be free of bubbles or delamination, and the crystalline silicon cell must not be displaced or aligned.

[0103] Table 1: Photoelectric parameters of the four-terminal perovskite crystalline silicon stacked cell modules prepared in Examples 1-2 and Comparative Examples 1-4 before and after encapsulation

[0104]

[0105]

[0106] As shown in Table 1, in the photoelectric performance test, the photoelectric conversion efficiency of the four-terminal perovskite crystalline silicon stacked cell modules prepared in Examples 1-2 and Comparative Examples 3-4 before and after encapsulation is not much different, while the photoelectric conversion efficiency of the four-terminal perovskite crystalline silicon stacked cell modules prepared in Comparative Examples 1-2 is severely attenuated before and after encapsulation. This is because in Comparative Example 1, there is no FTO glass as a barrier layer between the perovskite cell and the cross-linked EVA film, and the cross-linking agent in the cross-linked EVA film migrates and reacts with the perovskite material, causing the perovskite to degrade, resulting in a severe attenuation of the efficiency of the four-terminal perovskite crystalline silicon stacked cell module; in Comparative Example 2, high-temperature lamination at 160°C damages the perovskite material, and ultimately the efficiency of the four-terminal perovskite crystalline silicon stacked cell module is severely attenuated.

[0107] Table 2: Photoelectric parameters of the four-terminal perovskite crystalline silicon tandem cell modules prepared in Examples 1-2 and Comparative Examples 1-4 before and after UV15 aging

[0108]

[0109]

[0110] In the UV15 aging test, there are no appearance defects, and the power attenuation after the test does not exceed 8% of the initial value, which is qualified. As can be seen from Table 2, the four-terminal perovskite crystalline silicon stacked cell components prepared in Examples 1-2 and Comparative Examples 2-3 remain qualified, while the perovskite in the four-terminal perovskite crystalline silicon stacked cell components prepared in Comparative Examples 1 and 4 degrades. This is because the adhesive film used in the four-terminal perovskite crystalline silicon stacked cell components prepared in Examples 1-2 and Comparative Examples 2-3 is a UV-cutoff POE adhesive film, which blocks ultraviolet rays from entering the perovskite cell and prevents the degradation of the perovskite. However, the adhesive film used in the four-terminal perovskite crystalline silicon stacked cell components prepared in Comparative Examples 1 and 4 does not have a UV-cutoff function, and the perovskite cell will degrade under ultraviolet light.

[0111] Table 3: Insulation properties of four-terminal perovskite crystalline silicon stacked battery modules prepared in Examples 1-2 and Comparative Examples 1-4

[0112] <![CDATA[Insulation resistance (MΩ·m 2 )]]> Example 1 120 Example 2 120 Comparative Example 1 0.5 Comparative Example 2 120 Comparative Example 3 120 Comparative Example 4 120

[0113] As can be seen from Table 3, in the high temperature (85°C) insulation test, the four-terminal perovskite crystalline silicon stacked cell components prepared in Examples 1-2 and Comparative Examples 2-4 have excellent insulation effects, while the insulation performance of the four-terminal perovskite crystalline silicon stacked cell components prepared in Comparative Example 1 fails. This is because in the four-terminal perovskite crystalline silicon stacked cell components prepared in Examples 1-2 and Comparative Examples 2-4, the perovskite cell and the crystalline silicon cell are blocked by FTO glass, and the two belong to independent chambers, and the cross-linking agent in the cross-linked adhesive film in the crystalline silicon cell will not contact and react with the perovskite cell. In the four-terminal perovskite crystalline silicon stacked cell component prepared in Comparative Example 1, there is only one layer of adhesive film between the perovskite cell and the crystalline silicon cell. The adhesive film may partially melt at high temperatures, which greatly increases the risk of short circuit between the perovskite cell and the crystalline silicon cell. From the test results, the test resistance between the perovskite cell and the crystalline silicon cell in Comparative Example 1 is much less than 40MΩ·m 2 The test resistance between the perovskite cell and the crystalline silicon cell in Examples 1-2 and Comparative Examples 2-4 is much greater than 40MΩ·m 2 The insulation test results meet the requirements.

[0114] The results of the 120°C thermal baking observations show that when thermally baked at 120°C, the four-terminal perovskite crystalline silicon tandem cell modules produced in Examples 1-2, Comparative Examples 1-2, and Comparative Example 4 maintained structural stability, while the four-terminal perovskite crystalline silicon tandem cell module produced in Comparative Example 3 exhibited crystalline silicon cell displacement failure. This is because the adhesive film used in the four-terminal perovskite crystalline silicon tandem cell modules produced in Examples 1-2, Comparative Examples 1-2, and Comparative Example 4 was a cross-linked EVA film, which ensured that the crystalline silicon cell panels would not shift and be paralleled during outdoor operation. However, the adhesive film used in the four-terminal perovskite crystalline silicon tandem cell module produced in Comparative Example 3 was a non-cross-linked POE film, which could not prevent the film from melting and creeping at high temperatures, and could not prevent the crystalline silicon cell panels from shifting.

[0115] Table 4: Comprehensive comparative performance of the four-terminal perovskite crystalline silicon stacked battery components prepared in Examples 1-2 and Comparative Examples 1-4

[0116] efficiency 120℃ hot baking UV15 aging Insulation testing Example 1 constant qualified qualified qualified Example 2 constant qualified qualified qualified Comparative Example 1 Severe attenuation qualified Perovskite degradation Failure Comparative Example 2 Severe attenuation qualified qualified qualified Comparative Example 3 constant Displacement failure of crystalline silicon solar cells qualified qualified Comparative Example 4 constant qualified Perovskite degradation qualified

[0117] In summary, by adopting a new type of stacked battery structure, using transparent metal oxide as a barrier layer and using adhesive films with different functions, the short circuit problem between the perovskite battery circuit and the crystalline silicon battery circuit is avoided; the contact reaction between the perovskite and the cross-linking agent in the adhesive film is avoided; ultraviolet light is prevented from entering the perovskite battery and causing damage to the battery; and the displacement and paralleling problem of battery cells at high temperatures is avoided, ultimately effectively improving the reliability of the four-terminal perovskite crystalline silicon stacked battery module.

Claims

1. A four-terminal perovskite crystalline silicon stacked battery component, characterized in that: The four-terminal perovskite crystalline silicon stacked cell assembly comprises, in sequence, a front cover, a film a, a perovskite cell, a transparent metal oxide glass, a film b, a crystalline silicon cell, a film c, and a back cover; The adhesive film a is a non-crosslinked polyolefin elastomer; the adhesive film b is made of a crosslinked polyolefin elastomer and / or a crosslinked polyethylene-polyvinyl acetate copolymer; the adhesive film c is made of a crosslinked polyolefin elastomer and / or a crosslinked polyethylene-polyvinyl acetate copolymer; The cross-linked polyolefin elastomer is formed by cross-linking a cross-linkable polyolefin elastomer and a cross-linking agent; The cross-linked polyethylene-polyvinyl acetate copolymer is formed by cross-linking a cross-linkable polyethylene-polyvinyl acetate copolymer and a cross-linking agent.

2. The four-terminal perovskite crystalline silicon stacked battery assembly according to claim 1, characterized in that: The four-terminal perovskite crystalline silicon stacked cell assembly has one or more of the following characteristics: The thickness of the adhesive film a is 0.1-1 mm; The thickness of the transparent metal oxide glass is 0.2-3.2 mm; The thickness of the adhesive film b is 0.1-1 mm; The thickness of the adhesive film c is 0.1-1 mm; The cross-linkable polyolefin elastomer is a polyolefin elastomer that can be cross-linked by ultraviolet radiation or a polyolefin elastomer that can be cross-linked by heat; The cross-linkable polyethylene-polyvinyl acetate copolymer is a polyethylene-polyvinyl acetate copolymer that can be cross-linked by ultraviolet radiation or a polyethylene-polyvinyl acetate copolymer that can be cross-linked by heat; The cross-linking agent is a thermal cross-linking agent or an ultraviolet radiation cross-linking agent; The thermal crosslinking agent is a peroxide, preferably di-tert-butyl peroxide and / or dicumyl peroxide; The ultraviolet radiation crosslinking agent is a benzophenone photoinitiator and / or an inorganic powder composite photoinitiator, preferably one or more selected from benzophenone, 4-lauroyloxydibenzoyl ketone, antimony-doped tin oxide and rutile titanium dioxide; The transparent metal oxide glass is indium tin oxide glass or fluorine-doped tin oxide glass.

3. The four-terminal perovskite crystalline silicon stacked battery assembly according to claim 1, characterized in that: The four-terminal perovskite crystalline silicon stacked cell assembly further includes a packaging component; the packaging component is located between the transparent metal oxide glass and the front cover; and the packaging component is in a ring structure.

4. The four-terminal perovskite crystalline silicon stacked battery assembly according to claim 3, characterized in that: The packaging component is made of butyl rubber.

5. A method for preparing a four-terminal perovskite crystalline silicon stacked battery component, characterized in that: The method comprises the following steps: (1) First, a front cover plate, a film a precursor, a perovskite cell, and a transparent metal oxide glass are stacked in order from top to bottom, and then laminated to obtain a perovskite component; (2) stacking the perovskite component, the adhesive film b precursor, the crystalline silicon cell, the adhesive film c precursor and the back cover in order from top to bottom, laminating them, and finally irradiating them with ultraviolet light from the back cover to obtain a four-terminal perovskite crystalline silicon stacked cell component; or (1') stacking transparent metal oxide glass, adhesive film b precursor, crystalline silicon cell, adhesive film c precursor and rear cover plate in order from top to bottom, and then laminating to obtain a crystalline silicon module; (2') growing a perovskite cell on the transparent metal oxide glass of the crystalline silicon component to obtain an intermediate, stacking a front cover plate, a film a precursor and the intermediate in order from top to bottom, and then laminating to obtain a four-terminal perovskite crystalline silicon stacked cell component; Among them, the film a precursor is converted into film a; the film b precursor is converted into film b; the film c precursor is converted into film c; The film a precursor is a non-crosslinked polyolefin elastomer; The film b precursor comprises a cross-linkable polyolefin elastomer and / or a cross-linkable polyethylene-polyvinyl acetate copolymer; The adhesive film C precursor comprises a cross-linkable polyolefin elastomer and / or a cross-linkable polyethylene-polyvinyl acetate copolymer.

6. The method according to claim 5, wherein In step (1), the lamination temperature is 90-120°C; and / or In step (2), the lamination temperature is 90-120°C.

7. The method according to claim 5, wherein In step (1'), the lamination temperature is 140-160°C; and / or In step (2'), the lamination temperature is 90-120°C.

8. The method according to claim 5, wherein The method has one or more of the following characteristics: In step (2), the adhesive film b precursor further comprises an ultraviolet radiation crosslinking agent; In step (2), the adhesive film c precursor further comprises an ultraviolet radiation crosslinking agent; In step (2), the cross-linkable polyolefin elastomer is a polyolefin elastomer that can be cross-linked by ultraviolet light; In step (2), the cross-linkable polyethylene-polyvinyl acetate copolymer is a polyethylene-polyvinyl acetate copolymer that can be cross-linked by ultraviolet light.

9. The method according to claim 5, wherein The method has one or more of the following characteristics: In step (1'), the adhesive film b precursor further comprises a thermal crosslinking agent or an ultraviolet radiation crosslinking agent; In step (1'), the adhesive film c precursor further comprises a thermal crosslinking agent; In step (1'), the cross-linkable polyolefin elastomer is a polyolefin elastomer that can be cross-linked by ultraviolet radiation or a polyolefin elastomer that can be cross-linked by heat; In step (1'), the cross-linkable polyethylene-polyvinyl acetate copolymer is a polyethylene-polyvinyl acetate copolymer that can be cross-linked by ultraviolet radiation or a polyethylene-polyvinyl acetate copolymer that can be cross-linked by heat.

10. The method according to claim 9, wherein In step (1'), the film b precursor contains a thermal crosslinking agent, the film c precursor contains a thermal crosslinking agent, the crosslinkable polyolefin elastomer is a thermally crosslinkable polyolefin elastomer, and the crosslinkable polyethylene-polyvinyl acetate copolymer is a thermally crosslinkable polyethylene-polyvinyl acetate copolymer.

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