Flexible perovskite photovoltaic cell and method of encapsulating the same

Abstract

The application discloses a flexible perovskite photovoltaic cell and a packaging method thereof, and belongs to the technical field of perovskite photovoltaic cells. The technical problem to be solved is to reduce the water vapor permeability of the edge of a flexible perovskite photovoltaic cell assembly under the condition that butyl glue is not used and the packaging edge margin is super-narrow. The technical solution points are as follows: a flexible perovskite photovoltaic cell, comprising a water and oxygen barrier film, a glue layer, a flexible perovskite photovoltaic cell piece and a barrier layer; the barrier layer is composed of an inner layer, an intermediate layer and an outer layer; wherein: the inner layer comprises a polymer and a sheet material; the intermediate layer comprises a polymer, hollow SiO2 microspheres and a sheet material; and the outer layer comprises a polymer and fluorinated SiO2.

Description

Technical Field

[0001] This invention provides a flexible perovskite photovoltaic cell and its encapsulation method, belonging to the field of perovskite photovoltaic cell technology. Background Technology

[0002] For understanding the technical content of this invention:

[0003] Water vapor infiltration at the edges of perovskite solar cells has been a key factor restricting their development. Water vapor infiltration can cause chemical reactions in the internal materials of the cell, affecting its performance and lifespan. Encapsulation is one of the best methods to solve the stability problems of perovskite solar cells and extend device lifespan. Reliable encapsulation technology can achieve excellent sealing, creating a stable operating environment that prevents the intrusion of external water and oxygen, and also blocks the leakage of cell decomposition products from the system.

[0004] For example, in the widely used OPV product solution of combining water and oxygen barrier membranes with UV-curing adhesives, the adhesive has a high water vapor permeability (typically 3-6 g / m² for high-barrier adhesives). 2 For ordinary adhesives, the water vapor permeability is 10-20 g / m². 2 The low-temperature encapsulation film (EVA, POE, EPE) used in photovoltaic products poses a significant risk to long-term applications. Currently, encapsulation technologies combining polyisobutylene, polyolefin low-temperature encapsulation films, and glass have enabled glass-based perovskite solar cells to exhibit excellent durability. The dense arrangement of side methyl groups in the butyl rubber molecular chain restricts the thermal motion of polymer molecules, resulting in lower water vapor permeability (10). -2 g / m 2 / day), with good airtightness.

[0005] In fields such as mobile phone charging cases, laptop / e-reader power extensions, wireless charging, and Internet of Things (IoT) devices, perovskite batteries not only require stability but also small size (some less than 5cm). 2 Flexible perovskite photovoltaic cells are lightweight, thin, aesthetically pleasing, and have narrow encapsulation margins (≤5mm). The commonly used encapsulation method for flexible perovskite photovoltaic cells, which combines ultra-high water and oxygen barrier films with polyolefin films and butyl rubber, does not meet the requirements in terms of appearance and size. Furthermore, the butyl rubber edge is typically 1cm wide, significantly reducing the effective area of ​​the cell. Removing the butyl rubber edge seal to achieve an ultra-narrow encapsulation margin places even higher demands on the edge water vapor barrier performance of flexible perovskite photovoltaic cells.

[0006] The above requirements can be met by using a TFE in-line thin-film encapsulation solution similar to that used in OLED products. However, multi-layer (4-6 layers) structural designs, such as using a stacked barrier film with alternating inorganic (Al2O3, SiO2, SiNx) / organic (polyacrylate) deposition, reduce WVTR to 10-6 g / m 2 / day or less (such as Mitsui Chemicals' Flex™ series in the United States). However, this solution involves complex processes, expensive equipment, high costs, and long processing times, making it unsuitable for the current trend of popularizing and making affordable flexible photovoltaic products.

[0007] Chinese patent CN118632552A discloses a high-efficiency flexible perovskite photovoltaic cell encapsulation method. However, the patent mainly describes a method for preparing a water-blocking film that can be applied. The cell in this scheme is a small-sized unit cell. The encapsulation scheme does not mention any protection against edge moisture leakage. It only provides efficiency retention after 100 hours at 25°C and 85%RH, and does not disclose the long-term empirical efficiency retention rate.

[0008] Therefore, how to effectively solve the problem of water vapor penetration at the edges of flexible perovskite photovoltaic cells under the conditions of no butyl adhesive and ultra-narrow encapsulation margin is a technical problem that urgently needs to be solved. Summary of the Invention

[0009] The purpose of this invention is to provide:

[0010] A flexible perovskite photovoltaic cell and its encapsulation method, and related technologies, to solve technical problems such as reducing the edge water vapor permeability of flexible perovskite photovoltaic cells without using butyl adhesive and with ultra-narrow encapsulation margins, or a combination thereof.

[0011] Terminology Explanation:

[0012] Unless otherwise defined, all technical terms in this document have the same meaning as commonly understood by one of ordinary skill in the art to which the subject matter of the claims pertains. Unless otherwise stated, all patents, patent inventions, and disclosures cited in this document are incorporated herein by reference in their entirety. If multiple definitions exist for terms in this document, the definitions in this chapter shall prevail.

[0013] It should be understood that the above brief description and the following detailed description are exemplary and for illustrative purposes only, and do not limit the subject matter of the invention in any way. In this invention, the singular is used in conjunction with the plural unless otherwise specifically stated. It should also be noted that, unless otherwise stated, the use of “or” or “or” means “and / or”. Furthermore, the use of the term “comprising” and other forms such as “including,” “containing,” and “contains” are not limiting.

[0014] The definition of the standard chemical term can be found in the reference "Perovskite Solar Cells, edited by Xiao Lixin, Zou Dechun, et al., Peking University Press".

[0015] Unless otherwise stated, conventional methods within the scope of the art, such as water vapor permeability detection, contact angle detection, photoelectric conversion efficiency detection, and photoelectric conversion efficiency retention rate, shall be used.

[0016] Unless specifically defined herein, the use of all commercially available products herein employs standard techniques. For example, it may be carried out using the manufacturer's instructions for use with the kit, or in accordance with methods known in the art or the description of this invention. The techniques and methods described herein can generally be implemented according to conventional methods well known in the art, based on the descriptions in the various summary and more specific documents cited and discussed in this specification.

[0017] The term "flexible perovskite photovoltaic cell" as used in this article refers to a novel thin-film photovoltaic cell, belonging to the third generation of photovoltaic cells. It uses organometallic halides, inorganic metal halides, or organic / inorganic metal halides with a perovskite crystal structure (the same as the CaTiO3 crystal structure) as the photosensitive layer, and unlike traditional cells that use transparent glass as a substrate, it is made using flexible substrate materials such as PET, PEN, and PI.

[0018] Unless otherwise specified, the term "content" as used in this article refers to mass percentage.

[0019] In a first aspect, the present invention provides: a flexible perovskite photovoltaic cell, comprising, from bottom to top, a window water and oxygen barrier film, an upper adhesive layer, a flexible perovskite photovoltaic cell, a barrier layer, a lower adhesive layer, and a bottom water and oxygen barrier film; wherein the barrier layer is a three-layer organic-inorganic hybrid layer deposited layer by layer, comprising, from bottom to top, an inner layer, a middle layer, and an outer layer; wherein the inner layer is a polymer and sheet material composite layer; wherein the middle layer is an alternating layer of polymer, hollow SiO2 microspheres, and sheet material; and wherein the outer layer is a polymer and fluorinated SiO2 enriched layer.

[0020] The technically characteristic polymer is selected from: fluorocarbon polymer coating liquid, including fluorinated resins and solvents.

[0021] The preferred fluorinated resin is selected from at least one of polytetrafluoroethylene (PTFE), perfluoropolyether acrylate (PFPE-Acrylate), or fluorinated polyurethane (FPU).

[0022] The preferred solvent for the technical features is a perfluoroether solvent.

[0023] The preferred technical feature of the perfluoroether solvent is at least one of perfluoropolyether oil and perfluoro(2-butyltetrahydrofuran).

[0024] The mass ratio of fluorinated resin and solvent in the technical feature is selected from (5-20): (70-85).

[0025] The preferred mass ratio of the fluorinated resin and solvent is 20:70, 5:82, 5:85, 5:80, 20:71, or any combination thereof.

[0026] The sheet material is selected from at least one of the following: graphene, graphene oxide, montmorillonite, boron nitride, or nano-mica.

[0027] Among them, the preferred aspect ratio of the sheet material is >100.

[0028] Among them, the hollow SiO2 microspheres are selected from those with a particle size of 50-100nm and a shell thickness of 5-15nm.

[0029] The mass ratio of the hollow SiO2 microspheres and sheet material in the intermediate layer of the technical feature is selected from 1:1 to 2:1.

[0030] The preferred mass ratio of the hollow SiO2 microspheres and sheet material in the intermediate layer of the technical feature is 1:1, 1.5:1, 2:1, or any combination thereof.

[0031] Among them, the technical feature of fluorinated SiO2 is selected from: surface-modified -CF3 groups.

[0032] The preferred technical feature of fluorinated SiO2 is a particle size of 10-20 nm.

[0033] The technical features include an inner, middle, and outer layer, which also include a silane coupling agent.

[0034] The silane coupling agent is selected from: fluorinated silane coupling agents, specifically at least one of heptadecafluorodecyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, 1H,1H,2H,2H-perfluorooctyltrimethoxysilane, and 1H,1H,2H,2H-perfluorodecyltrimethoxysilane.

[0035] The proportions of the inner layer of the technical feature are selected from: 85-91% polymer, 1-8% sheet material, and 1-8% silane coupling agent.

[0036] The preferred ratio of the inner layer of the technical features is: 90-91% polymer, 1-5% sheet material, and 1-5% silane coupling agent.

[0037] The optimal ratio of the inner layer of technical features is further optimized: 91% polymer, 4% sheet material, and 5% silane coupling agent.

[0038] The proportions of the intermediate layer in the technical feature are selected from: 90-95% polymer, 2%-6% hollow SiO2 microspheres, 1-5% sheet material, and 1-5% silane coupling agent.

[0039] The preferred ratio of the intermediate layer to the technical features is: 90-93% polymer, 2%-4% hollow SiO2 microspheres, 1-3% sheet material, and 1-4% silane coupling agent.

[0040] The proportions of the intermediate layer in the technical feature are selected from: 90% polymer, 4% hollow SiO2 microspheres, 2% sheet material, and 4% silane coupling agent.

[0041] The ratio of the outer layer of technical features is selected from: 85-95% polymer, 4%-10% fluorinated SiO2 and 1-5% silane coupling agent.

[0042] The preferred ratio of the outer layer of technical features is: 85-90% polymer, 8%-10% fluorinated SiO2 and 2-5% silane coupling agent.

[0043] The technical features of the water and oxygen barrier membrane include: transparent water and oxygen barrier materials and non-transparent water and oxygen barrier membranes.

[0044] Among them, the technical characteristic of the transparent water-oxygen barrier membrane is that its water vapor transmission rate (WVTR) is < 5 × 10⁻⁶. -3 g / m 2 / day.

[0045] The technical features of the transparent water and oxygen barrier material include: a coated substrate and a water and oxygen barrier layer.

[0046] The coating substrate is selected from at least one single-layer or multi-layer film layer of the following materials: polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene, polypropylene, polyimide, and polytetrafluoroethylene.

[0047] The thickness of the coating substrate is selected from 5-500μm.

[0048] The thickness of the substrate for the technical feature coating is preferably 12-100μm.

[0049] The technical feature of the water and oxygen barrier layer is selected from: an inorganic barrier layer or a pair of layers containing one or more inorganic / organic barrier layers.

[0050] The technical feature of the water and oxygen barrier layer is: an inorganic barrier layer or a paired layer containing one or more inorganic / organic barrier layers.

[0051] Among them, the non-transparent water and oxygen barrier film has the following technical features: an aluminum foil layer, a polymer substrate, and a double-sided weather-resistant layer.

[0052] Among them, the thickness of the aluminum foil layer is 10-40μm.

[0053] The technical feature polymer substrate is selected from polyethylene terephthalate.

[0054] The technical feature of the double-sided weather-resistant layer is selected from at least one of the following: fluorine-containing weather-resistant coating or fluorine-containing film.

[0055] The technical features of flexible perovskite photovoltaic cells include: a supporting substrate, a perovskite cell device functional layer, and a conductive tape.

[0056] The technical feature supporting substrate is selected from at least one single-layer or multi-layer film layer of polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene, polypropylene, and polyimide.

[0057] The thickness of the technical feature supporting substrate is 20-300μm.

[0058] Among them, the technical features of the perovskite solar cell device are selected from either the nip or pin structure.

[0059] Among them, the conductive tape with technical characteristics is a tin-plated copper tape containing pressure-sensitive conductive adhesive.

[0060] The technical features of the upper and lower adhesive layers are selected from at least one of the following: UV curing adhesive, thermosetting adhesive, POE film, or OCA film.

[0061] The technical feature barrier layer is selected from those with a total thickness of 0.5-10μm.

[0062] The preferred technical feature barrier layer has a total thickness of 1-5 μm.

[0063] Secondly, the present invention provides: a method for encapsulating flexible perovskite photovoltaic cells, comprising the following steps:

[0064] (1) The inner coating liquid, the middle coating liquid and the outer coating liquid are sequentially coated and cured on the back electrode surface of the flexible perovskite photovoltaic cell to obtain a flexible perovskite photovoltaic cell with a barrier layer.

[0065] (2) The surface of the flexible perovskite photovoltaic cell with a barrier layer is encapsulated by a combination of an adhesive layer and a water and oxygen barrier film.

[0066] Among them, the technical feature coating is selected from: wet heat coating.

[0067] The preferred technical feature of wet heat coating is at least one of spraying, scraping, slit coating, inkjet printing, and screen printing.

[0068] The amount of technical feature coating is selected from the dry thickness of the inner layer, intermediate layer and outer layer coatings, which is 0.4-2μm.

[0069] The curing of technical features is selected from the following: temperature 70-90℃, time 5-30min.

[0070] The technical feature of the inner coating liquid is selected from: 5%-20% fluorinated resin, 70%-85% solvent, 1%-5% sheet material, and 1%-5% silane coupling agent.

[0071] The intermediate coating liquid is selected from: 5%-20% fluorinated resin, 70%-85% solvent, 1%-5% sheet material, 2%-6% hollow SiO2 microspheres, and 1%-5% silane coupling agent.

[0072] The outer coating liquid, as a technical feature, is selected from: 5%-20% fluorinated resin, 70%-85% solvent, 5%-10% fluorinated SiO2, and 1%-5% silane coupling agent.

[0073] Among them, the combination of technical features is selected from: lamination or UV / thermosetting encapsulation.

[0074] The technical features include a lamination temperature of 105-120℃, a pressure of 60-90kPa, and a time of 10-30min;

[0075] Among them, the curing time of UV-curable or thermosetting adhesives is 5-30 minutes.

[0076] Thirdly, the present invention provides: a flexible photovoltaic product, comprising the above-mentioned flexible perovskite photovoltaic cell.

[0077] The beneficial effects of this invention are as follows:

[0078] (1) The barrier layer of the present invention forms a 3D barrier network with a "maze effect" through the synergistic effect of multi-scale fillers and the layer-by-layer deposition process. The hollow structure extends the diffusion path and achieves high water and oxygen barrier performance of the coating, which is superior to the multi-scale filler blend system, and achieves effective encapsulation and protection of the perovskite edge. After removing the edge butyl rubber, the encapsulation edge distance is 2-5mm, and the indoor storage time is increased from 3 months to 2 years or even longer.

[0079] (2) The barrier layer coating liquid of the present invention uses highly inert chemical raw materials that will not react with the perovskite battery. It can not only provide water and oxygen barrier function for the battery, but also provide insulation protection. When the busbar is arranged on the back of the battery, there is no need to apply additional insulating tape. This expands the application range of adhesive materials for perovskite encapsulation.

[0080] (3) The barrier layer of the present invention is a coating polymer / inorganic filler blend system, rather than the inorganic barrier layer prepared by traditional vacuum deposition. It is not only simple and low cost, but also greatly improves the flexibility of the battery and avoids the problem that the inorganic barrier layer is brittle and easily damaged during operation.

[0081] Furthermore, based on the present invention:

[0082] Based on the comparison of Examples 1-5 and Comparative Examples 1-6, this invention achieves new technical effects by using a combination of specific materials and dosage relationships for the inner, middle, and outer layers, including barrier layers: reducing the water vapor permeability at the edges of flexible perovskite photovoltaic cells without using butyl sealant and while achieving ultra-narrow encapsulation margins. The combined technical effect is superior to the sum of the effects of each individual technical method. Attached Figure Description

[0083] Figure 1 This is a schematic diagram of the structure of the flexible perovskite photovoltaic cell of the present invention, wherein 1-window water and oxygen barrier film, 2-upper adhesive layer, 3-flexible perovskite photovoltaic cell, 4-barrier layer, 5-lower adhesive layer, and 6-bottom water and oxygen barrier film.

[0084] Figure 2 This is a partial structural diagram of the flexible perovskite photovoltaic cell of the present invention, wherein 31 is the flexible perovskite photovoltaic cell substrate and 32 is the flexible perovskite photovoltaic cell functional layer. Detailed Implementation

[0085] The following non-limiting embodiments are intended to enable those skilled in the art to gain a more comprehensive understanding of the present invention, but do not limit the invention in any way. The following content is merely an exemplary description of the scope of protection claimed by the present invention, and those skilled in the art can make various changes and modifications to the present invention based on the disclosed content, and such changes should also fall within the scope of protection claimed by the present invention.

[0086] The present invention will be further described below by way of specific embodiments. Unless otherwise specified, all instruments, devices, equipment, reagents, products, etc., used in the embodiments of the present invention are obtained through conventional commercial means.

[0087] Preparation method:

[0088] (1) A barrier layer inner coating liquid is applied to the surface of the back electrode of a flexible perovskite photovoltaic cell and cured to form an inner layer.

[0089] (2) In step (1), a barrier intermediate layer coating liquid is applied to the upper surface of the inner layer of the barrier layer, and the intermediate layer is formed after curing.

[0090] (3) Apply the outer layer coating liquid of the barrier layer to the upper surface of the middle layer of the barrier layer in step (2), and form the outer layer after curing.

[0091] Steps (1)-(3) yield a flexible perovskite photovoltaic cell with a barrier layer.

[0092] (4) The surface of the flexible perovskite photovoltaic cell with a barrier layer is encapsulated by a combination of an adhesive layer and a water-oxygen barrier film. After encapsulation, as shown... Figure 1 The upper and lower surface water-oxygen barrier films are the window water-oxygen barrier film and the bottom water-oxygen barrier film, respectively. The adhesive layer connecting the window water-oxygen barrier film to the surface of the flexible perovskite photovoltaic cell with the barrier layer is the upper adhesive layer; the adhesive layer connecting the bottom water-oxygen barrier film to the surface of the flexible perovskite photovoltaic cell with the barrier layer is the lower adhesive layer.

[0093] If an adhesive film is used as the encapsulation layer: place the laid material into a laminator, laminate at 115℃, laminate at 80KPa, and laminate for 20 minutes. After cooling, the flexible perovskite photovoltaic cell encapsulation is complete.

[0094] If using a coating adhesive as the encapsulation layer: Lay the prepared material through a roller, then UV-cur it with UVA at 365nm and a curing energy of 4000mJ / cm². 2 The flexible perovskite photovoltaic cell encapsulation was completed.

[0095] If OCA film is used as the adhesive layer for encapsulation: the laid material is rolled and laminated at 70°C to complete the encapsulation of flexible perovskite photovoltaic cells.

[0096] Example 1

[0097] Example 1 consists of the following structure:

[0098] (1) Window water-oxygen barrier membrane (WVTR < 1×10 -3 g / m 2 / day @38℃, 100 RH% thickness 135μm).

[0099] (2) Top layer: POE film (Raybo series, thermoplastic POE, 200g / m²) 2 ).

[0100] (3) Flexible perovskite photovoltaic cell (self-made): FlexAurora 01 model.

[0101] (4) Barrier layer, including inner layer, middle layer and outer layer.

[0102] ①Inner layer (physical barrier layer)

[0103] PTFE resin (Chemours Teflon® PTFE 6C: particle size 25μm), content 18%;

[0104] Perfluorinated (2-butyltetrahydrofuran) solvent (3M FC-75), content 73%;

[0105] Boron nitride nanosheets (Saint-Gobain BNX20, 10 μm particle size), content 4%;

[0106] 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (Gelest SIH5841.5), content 5%.

[0107] (Spraying: Coating thickness 1.2μm, cure at 80℃ for 5min)

[0108] ②Middle layer (3D maze layer):

[0109] PTFE resin (Chemours Teflon® PTFE 6C: particle size 25μm), content 15%;

[0110] Perfluoropolyether oil (Solvay Fomblin® Y LVAC), content 72%;

[0111] Hollow SiO2 microspheres (Asahi Glass Aerosil® H200, Japan) / graphene oxide (Changzhou Sixth Element SE2430 = 1.8:1, total content 8%);

[0112] Silane coupling agent (Shin-Etsu Chemical KBM-7803), content 5%.

[0113] (Scraping: Coating thickness 1μm, cure at room temperature for 30min)

[0114] ③Outer layer (hydrophobic protective layer):

[0115] Fluorinated polyurethane (Daikin Unidyne® TG-551), content 20%;

[0116] Perfluorinated (2-butyltetrahydrofuran) solvent (3M FC-75), 70% purity;

[0117] -CF3-modified SiO2 (Evonik AEROSIL® R812), content 8%;

[0118] Silane coupling agent (Shin-Etsu Chemical KBM-7803), content 2%;

[0119] (5) Lower adhesive layer: POE film (Raybo series, thermoplastic POE, 200g / m²)2 ).

[0120] (6) Bottom water-oxygen barrier membrane (WVTR < 1×10 -3 g / m 2 / day @38℃, 100 RH%, thickness 135μm), package margin 5mm.

[0121] The above contents are: the percentage of the inner layer material mass to the total inner layer mass; the percentage of the middle layer material mass to the total middle layer mass; and the percentage of the outer layer material mass to the total outer layer mass.

[0122] Example 2

[0123] Example 2 consists of the following structure:

[0124] (1) The battery device structure is: a window water-oxygen barrier membrane (WVTR < 5 × 10⁻⁶). -4 g / m 2 / day @38℃, 100 RH%, thickness 210μm).

[0125] (2) Top layer: UV curing adhesive (German Petres ELPEGUARD®DSL1600E-FLZ / 757).

[0126] (3) Flexible perovskite photovoltaic cell (self-made): FlexAurora 01 model.

[0127] (4) The barrier layer includes an inner layer, a middle layer and an outer layer.

[0128] ①Inner layer (physical barrier layer)

[0129] PFPE-Acrylate (Solvay Fluorolink® AD1700), content 18%;

[0130] Perfluorinated (2-butyltetrahydrofuran) solvent (3M FC-75), content 73%;

[0131] Boron nitride nanosheets (Saint-Gobain BNX20, 10 μm particle size), content 4%;

[0132] 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (Gelest SIH5841.5), content 5%.

[0133] (Spraying: Coating thickness 1.2μm, cure at 80℃ for 5min)

[0134] ②Middle layer (3D maze layer):

[0135] PFPE-Acrylate (Solvay Fluorolink® AD1700), 15% content;

[0136] Perfluoropolyether oil (Solvay Fomblin® Y LVAC), content 72%;

[0137] Hollow SiO2 microspheres (Asahi Glass Aerosil® H200, Japan) / graphene oxide (Changzhou Sixth Element SE2430 = 1.8:1, total content 8%);

[0138] Silane coupling agent (Shin-Etsu Chemical KBM-7803), content 5%.

[0139] (Scraping: Coating thickness 1μm, cure at room temperature for 30min)

[0140] ③Outer layer (hydrophobic protective layer):

[0141] PFPE-Acrylate (Solvay Fluorolink® AD1700), 20% content;

[0142] Perfluorinated (2-butyltetrahydrofuran) solvent (3M FC-75), 70% purity;

[0143] -CF3-modified SiO2 (Evonik AEROSIL® R812), content 8%;

[0144] Silane coupling agent (Shin-Etsu Chemical KBM-7803), content 2%.

[0145] (Spraying: Coating thickness 0.8μm, cured at 50℃ for 15min)

[0146] The above contents are: the percentage of the inner layer material mass to the total inner layer mass; the percentage of the middle layer material mass to the total middle layer mass; and the percentage of the outer layer material mass to the total outer layer mass.

[0147] (5) Underlying adhesive layer: UV curing adhesive (Petres ELPEGUARD®DSL1600E-FLZ / 75, Germany)

[0148] (6) Bottom water-oxygen barrier membrane: WVTR < 5 × 10 -4 g / m 2 / day @38℃, 100 RH%, thickness 210μm, package margin 3mm.

[0149] Example 3

[0150] Example 3 consists of the following structure:

[0151] (1) The battery device structure is: a window water-oxygen barrier membrane (WVTR < 5 × 10⁻⁶). -4 g / m 2 / day @38℃, 100% RH, thickness 210μm)

[0152] (2) Top layer: POE film (Raybo series, thermoplastic POE, 200g / m2)

[0153] (3) Flexible perovskite photovoltaic cell (self-made): FlexAurora 01 model.

[0154] (4) Barrier layer, including inner layer, middle layer and outer layer.

[0155] ①Inner layer (physical barrier layer)

[0156] PTFE resin (Chemours Teflon® PTFE 6C: particle size 25μm), content 20%;

[0157] Perfluorinated (2-butyltetrahydrofuran) solvent (3MFC-75), 70% content;

[0158] Boron nitride nanosheets (Saint-Gobain BNX20, 10 μm particle size), content 5%;

[0159] 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (GelestSIH5841.5), content 5%;

[0160] (Spraying: Coating thickness 1.5μm, cure at 80℃ for 5min)

[0161] ②Middle layer (3D maze layer):

[0162] PTFE resin (Chemours Teflon® PTFE 6C: particle size 25μm), content 5%;

[0163] Perfluoropolyether oil (Solvay Fomblin® Y LVAC), content 82%;

[0164] Hollow SiO2 microspheres (Asahi Glass Aerosil® H200, Japan) / Graphene oxide (Changzhou Sixth Element SE2430 = 1:1, total content 8%);

[0165] Silane coupling agent (Shin-Etsu Chemical KBM-7803), content 5%.

[0166] (Scraping: Coating thickness 0.5μm, cure at room temperature for 30min)

[0167] ③Outer layer (hydrophobic protective layer):

[0168] Fluorinated polyurethane (Daikin Unidyne® TG-551), content 20%;

[0169] Perfluorinated (2-butyltetrahydrofuran) solvent (3M FC-75), 70% purity;

[0170] -CF3-modified SiO2 (Evonik AEROSIL® R812), content 8%;

[0171] Silane coupling agent (Shin-Etsu Chemical KBM-7803), content 2%.

[0172] (Spraying: Coating thickness 1μm, cure at 50℃ for 15min)

[0173] (5) Lower adhesive layer: POE film (Raybo series, thermoplastic POE, 200g / m²) 2 ).

[0174] (6) Bottom water-oxygen barrier membrane (WVTR < 5 × 10 -4 g / m 2 / day @38℃, 100 RH%, thickness 210μm), package margin 4mm.

[0175] Example 4

[0176] The battery device structure is as follows: a window water-oxygen barrier membrane (WVTR < 5 × 10⁻⁶). -4 g / m 2 / day @38℃, 100 RH%, thickness 210μm).

[0177] (2) Top layer: UV curing adhesive (German Petres ELPEGUARD®DSL1600E-FLZ / 757).

[0178] (3) Flexible perovskite photovoltaic cell (self-made): FlexAurora 01 model.

[0179] (4) Barrier layer, including inner layer, middle layer and outer layer.

[0180] ①Inner layer (physical barrier layer)

[0181] Fluorinated polyurethane (Daikin Unidyne® TG-551), content 6%;

[0182] Perfluorinated (2-butyltetrahydrofuran) solvent (3M FC-75), 85% purity;

[0183] Boron nitride nanosheets (Saint-Gobain BNX20, 10 μm particle size), content 4%;

[0184] 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (Gelest SIH5841.5), content 5%.

[0185] (Spraying: Coating thickness 0.5μm, cure at 80℃ for 5min)

[0186] ②Middle layer (3D maze layer):

[0187] Fluorinated polyurethane (Daikin Unidyne® TG-551), content 5%;

[0188] Perfluoropolyether oil (Solvay Fomblin® Y LVAC), 80% content;

[0189] Hollow SiO2 microspheres (Asahi Glass Aerosil® H200, Japan): Graphene oxide (Changzhou Sixth Element SE2430 = 1.8:1, total content 10%)

[0190] Silane coupling agent (Shin-Etsu Chemical KBM-7803), content 5%.

[0191] (Scraping: Coating thickness 0.4μm, cure at room temperature for 30min)

[0192] ③Outer layer (hydrophobic protective layer):

[0193] PFPE-Acrylate (Solvay Fluorolink® AD1700), 5% content;

[0194] Perfluorinated (2-butyltetrahydrofuran) solvent (3M FC-75), 80% purity;

[0195] -CF3-modified SiO2 (Evonik AEROSIL® R812), 10% content;

[0196] Silane coupling agent (Shin-Etsu Chemical KBM-7803), content 5%.

[0197] (5) Underlying adhesive layer: UV curing adhesive (Petres ELPEGUARD®DSL1600E-FLZ / 75, Germany)

[0198] (6) Bottom water-oxygen barrier membrane (WVTR < 5 × 10 -4 g / m 2 / day @38℃, 100% RH

[0199] Thickness 210μm), package margin 2mm.

[0200] Example 5

[0201] (1) The battery device structure is: a window water-oxygen barrier membrane (WVTR < 5 × 10⁻⁶). -4 g / m 2 / day @38℃, 100 RH%, thickness 210μm).

[0202] (2) Top layer: POE film (Raybo series, thermoplastic POE, 200g / m²) 2 ).

[0203] (3) Flexible perovskite photovoltaic cell (self-made): FlexAurora 01 model.

[0204] (4) Barrier layer, including inner layer, middle layer and outer layer.

[0205] ①Inner layer (physical barrier layer)

[0206] PTFE resin (Chemours Teflon® PTFE 6C: particle size 25μm), content 20%;

[0207] Perfluorinated (2-butyltetrahydrofuran) solvent (3M FC-75), content 71%;

[0208] Boron nitride nanosheets (Saint-Gobain BNX20, 10 μm particle size), content 4%;

[0209] 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (GelestSIH5841.5), content 5%.

[0210] (Spraying: Coating thickness 1.5μm, cure at 80℃ for 5min)

[0211] ②Middle layer (3D maze layer):

[0212] PTFE resin (Chemours Teflon® PTFE 6C: particle size 25μm), content 20%;

[0213] Perfluoropolyether oil (Solvay Fomblin® Y LVAC), 70% content;

[0214] Hollow SiO2 microspheres (Asahi Glass Aerosil® H200, Japan): Graphene oxide (Changzhou Sixth Element SE2430 = 2:1, total content 6%)

[0215] Silane coupling agent (Shin-Etsu Chemical KBM-7803), content 4%.

[0216] (Scraping: Coating thickness 1.5μm, cure at room temperature for 30min)

[0217] ③Outer layer (hydrophobic protective layer):

[0218] PTFE resin (Chemours Teflon® PTFE 6C: particle size 25μm), content 20%;

[0219] Perfluorinated (2-butyltetrahydrofuran) solvent (3M FC-75), 70% purity;

[0220] -CF3-modified SiO2 (Evonik AEROSIL® R812), content 8%;

[0221] Silane coupling agent (Shin-Etsu Chemical KBM-7803), content 2%.

[0222] (Spraying: Coating thickness 2μm, cure at 80℃ for 10min)

[0223] (5) Lower adhesive layer: POE film (Raybo series, thermoplastic POE, 200g / m²) 2 ).

[0224] (6) Bottom water-oxygen barrier membrane (WVTR < 5 × 10 -4 g / m 2 / day @38℃, 100 RH%, thickness 210μm), package margin 5mm.

[0225] Comparative Example 1

[0226] Compared with Example 1, the only difference is that Comparative Example 1 did not have a barrier layer prepared.

[0227] Comparative Example 2

[0228] Compared with Example 1, the only difference is that Comparative Example 2 has only an inner layer as the barrier layer, without a middle layer and an outer layer.

[0229] Comparative Example 3

[0230] Compared with Example 1, the only difference is that the barrier layer of Comparative Example 3 only has an inner layer and an outer layer, and no intermediate layer.

[0231] Comparative Example 4

[0232] Compared with Example 1, the only difference is that Comparative Example 4 has only an inner layer and a middle layer in its barrier layer, and no outer layer.

[0233] Comparative Example 5

[0234] Compared with Example 1, the only difference in Comparative Example 5 is that the barrier layer was replaced with a hydrophobic fluoropolymer (PiQ NANO nanocoating agent S1).

[0235] Comparative Example 6

[0236] Compared with Example 1, the only difference is the change in the amount of the inner layer used in Comparative Example 6:

[0237] Inner layer (physical barrier layer)

[0238] PTFE resin (Chemours Teflon® PTFE 6C: particle size 25μm), content 19%;

[0239] Perfluorinated (2-butyltetrahydrofuran) solvent (3M FC-75), 80% purity;

[0240] Boron nitride nanosheets (Saint-Gobain BNX20, 10 μm particle size), content 0.5%;

[0241] 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (Gelest SIH5841.5), content 0.5%.

[0242] (Spraying: Coating thickness 1.4μm, cure at 80℃ for 5min).

[0243] Detection Example 1

[0244] The following testing standards were used in the testing of this invention:

[0245] Water vapor transmission rate test standard: ASTM F1249 infrared sensor method (modulation type), American MOCONPERMATRAN-W® 3 / 33.

[0246] The standard for testing the contact angle with water is GB / T 30693-2014 (China) "Determination of the contact angle between plastic films and water", and Krüss DSA100 (Germany).

[0247] Battery photoelectric conversion efficiency testing standard: IEC 60904-1-2 (2023).

[0248] The test results are shown in Table 1.

[0249] Table 1

[0250]

[0251] In embodiments 1-5 of the present invention, the effective coating area of ​​the barrier layer is larger than the effective area of ​​the battery, and the perimeter distance between the barrier layer and the effective area of ​​the functional layer of the flexible perovskite photovoltaic cell is 1 mm.

[0252] The distance between the edge of the flexible water and oxygen barrier film and the edge of the flexible perovskite photovoltaic cell is 2-5 mm.

[0253] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, and is not intended to limit the scope of protection of the present invention. Simple modifications or equivalent substitutions made by those skilled in the art to the technical solution of the present invention do not depart from the essence and scope of the technical solution of the present invention.

Claims

1. A flexible perovskite photovoltaic cell, comprising, from bottom to top, a window water-oxygen barrier film, an upper adhesive layer, a flexible perovskite photovoltaic cell, a barrier layer, a lower adhesive layer, and a bottom water-oxygen barrier film, characterized in that, The barrier layer consists of an inner layer, a middle layer, and an outer layer from bottom to top; the inner layer is a composite layer of polymer and sheet material; the middle layer is an alternating layer of polymer, hollow SiO2 microspheres, and sheet material; and the outer layer is a polymer and fluorinated SiO2 enriched layer. The polymers of the inner, middle and outer layers are fluorocarbon polymer coating liquids, including fluorinated resins; the fluorinated resins are at least one of polytetrafluoroethylene, perfluoropolyether acrylate or fluorinated polyurethane. The inner, middle, and outer layers also include silane coupling agents; The inner layer comprises, by weight percentage, 85-91% polymer, 1-8% sheet material, and 1-8% silane coupling agent.

2. The flexible perovskite photovoltaic cell according to claim 1, characterized in that, The polymer also includes a solvent.

3. The flexible perovskite photovoltaic cell according to claim 1, characterized in that, The sheet material is at least one of graphene, graphene oxide, montmorillonite, boron nitride, or nanomica, with an aspect ratio >100.

4. The flexible perovskite photovoltaic cell according to claim 1, characterized in that, The fluorinated SiO2 is SiO2 with -CF3 groups modified on its surface, and the particle size is 10-20 nm; the hollow SiO2 microspheres have a particle size of 50-100 nm and a shell thickness of 5-15 nm.

5. The flexible perovskite photovoltaic cell according to claim 1, characterized in that, The intermediate layer comprises, by weight percentage, 90-95% polymer, 2%-6% hollow SiO2 microspheres, 1-5% sheet material and 1-5% silane coupling agent.

6. The flexible perovskite photovoltaic cell according to claim 1, characterized in that, The outer layer comprises, by weight percentage: 85-95% polymer, 4%-10% fluorinated SiO2 and 1-5% silane coupling agent.

7. The flexible perovskite photovoltaic cell according to claim 1, characterized in that, The total thickness of the barrier layer is 0.5-10 μm; The effective coating area of ​​the barrier layer is larger than the effective area of ​​the battery, and the perimeter distance is ≤1mm.

8. The encapsulation method for flexible perovskite photovoltaic cells according to any one of claims 1-7, characterized in that, Includes the following steps: (1) The inner layer, the middle layer and the outer layer are sequentially coated and cured on the back electrode surface of the flexible perovskite photovoltaic cell to obtain a flexible perovskite photovoltaic cell with a barrier layer. (2) The surface of the flexible perovskite photovoltaic cell with a barrier layer is encapsulated by a combination of adhesive layer, window water and oxygen barrier film and bottom water and oxygen barrier film.

9. A flexible photovoltaic product, characterized in that, Including the flexible perovskite photovoltaic cell as described in any one of claims 1-7.

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