Repair layer, perovskite solar cell, laminated cell and photovoltaic module

Abstract

The invention discloses a repair layer, a perovskite solar cell, a laminated cell and a photovoltaic module. The repair layer comprises a polymer matrix and a complex dispersed in the polymer matrix, the polymer matrix contains one or more of hydroxyl, primary amino, secondary amino, a dynamic borate bond, a disulfide bond, a Diels-Alder ring, an imine bond and a supramolecular polymer, and the complex comprises a porous carrier and a defect passivator. The defect passivating agent is loaded on the porous carrier, the defect passivating agent comprises one or more of alkyl ammonium iodized salt, a sulfur-containing passivating agent, purine alkaloid, organic phosphine oxide, guanidine salt and a chelating passivating agent, and the purine alkaloid contains carbonyl. Therefore, the repairing layer not only can repair physical cracks in the perovskite film layer, but also can repair chemical defects in the perovskite film layer.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of solar cells, in particular, to a repair layer, a perovskite solar cell, a stacked cell and a photovoltaic module. BACKGROUND

[0002] Perovskite solar cells are considered as a strong contender for the next generation of photovoltaic technology due to their outstanding photoelectric conversion efficiency (PCE, has broken 27%) and low manufacturing cost. However, its commercialization process is severely constrained by the long-term stability of the device. The perovskite material itself is highly sensitive to external factors such as humidity, oxygen, high temperature and ultraviolet light, and its inherent ionic crystal characteristics make it prone to brittle fracture under mechanical stress.

[0003] The stability challenge of current perovskite solar cells mainly comes from the following two types of damage: Physical damage: During manufacturing, packaging and long-term operation, mechanical stress inevitably induces microcracks in the perovskite thin film. These cracks will become non-radiative recombination centers, hinder carrier transport, and provide a path for the intrusion of humidity and oxygen, accelerating device degradation. Data shows that more than 50% of the cells will fail due to physical damage within 1000 hours under 85℃ / 85%RH humid heat accelerated aging test.

[0004] Chemical degradation: Humid heat environment will induce the extraction of volatile organic cations (such as methylamine ions) and the migration of iodine ions in the perovskite lattice, generating a large number of iodine vacancies (V I + ) defects. These deep level defects are the main carrier recombination centers, which will cause the open-circuit voltage (Voc) and fill factor (FF) of perovskite solar cells to decrease significantly, with an average annual efficiency decay rate of more than 15%.

[0005] Current repair technologies can usually only solve a single type of damage (physical or chemical), lack the ability to co-repair multiple damages in complex environments; in addition, the repair process often requires external intervention (such as solution immersion, specific light), the response speed is slow (for example, using MAI solution repair requires 30-50 seconds), and at high temperatures above 60℃, the repair function of many traditional repair materials will fail.

[0006] Therefore, developing a technology that can intelligently respond to real working environment (such as temperature and humidity changes) without external intervention, and can simultaneously and efficiently repair physical and chemical damage, is crucial for promoting the commercialization of perovskite solar cells. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007] The present application aims to alleviate or solve at least one of the above-mentioned problems to at least some extent. SUMMARY

[0007]

[0008] In an aspect of the present application, a repairing layer is provided. In some embodiments of the present application, the repairing layer comprises a polymer matrix and a complex dispersed in the polymer matrix, the polymer matrix contains one or more of hydroxyl group, primary amine group, secondary amine group, dynamic boronate ester bond, disulfide bond, Diels-Alder ring, imine bond, supramolecular polymer, and the complex comprises a porous carrier and a defect passivator, the porous carrier loads the defect passivator, and the defect passivator comprises one or more of hydrocarbyl ammonium iodide salt, sulfur-containing passivator, purine alkaloid, organophosphine oxide, guanidinium salt, and chelating passivator, and the purine alkaloid contains carbonyl group. Thus, the repairing layer can repair both physical cracks and chemical defects in the perovskite film layer.

[0009] In some embodiments of the present application, the polymer matrix satisfies one of the following conditions: the polymer matrix comprises polyacrylamide-polyethylene glycol hydrogel and contains dynamic boronate ester bond; the polymer matrix comprises polyurethane elastomer; the polymer matrix comprises polyvinyl alcohol-based hydrogel and contains dynamic boronate ester bond; the polymer matrix comprises chitosan and / or alginate and contains dynamic boronate ester bond; the polymer matrix comprises polyurea or polyurethane and contains disulfide bond; the polymer matrix contains Diels-Alder ring and imine bond; and the polymer matrix comprises supramolecular polymer containing cyclodextrin host and adamantane guest.

[0010] In some embodiments of the present application, the defect passivator satisfies at least one of the following conditions: the hydrocarbyl ammonium iodide salt comprises one or more of hexylammonium iodide and phenethylammonium iodide; the sulfur-containing passivator comprises one or more of thiourea and L-cysteine; the purine alkaloid comprises one or more of caffeine, theophylline, and theobromine; the organophosphine oxide comprises one or more of trioctylphosphine oxide, triethylphosphine oxide, and tributylphosphine oxide; the guanidinium salt comprises guanidinium iodide; and the chelating passivator comprises one or more of ethylenediaminetetraacetic acid and crown ether. The above-mentioned defect passivators can all repair chemical defects in the perovskite film layer, thereby effectively inhibiting non-radiative recombination.

[0011] In some embodiments of the present application, the porous carrier comprises one or more of zeolitic imidazolate framework and mesoporous silica. The above-mentioned porous carrier has abundant pore structure, can load more defect passivators, and release the defect passivators under certain conditions (e.g., heating conditions).

[0012] In some embodiments of the present application, the repairing layer satisfies at least one of the following conditions: the thickness of the repairing layer is 20-50 nm; the repairing layer comprises a plurality of microchannels extending in the thickness direction; and the mass content of the composite is 5-25% based on the total mass of the repairing layer.

[0013] In some embodiments of the present application, the repairing layer satisfies at least one of the following conditions: the pore size of the microchannels is 50-100 nm; the spacing between the centers of two adjacent microchannels is 200-500 nm; and the cross section of the microchannels perpendicular to the thickness direction of the repairing layer is circular, elliptical, polygonal or irregular. In this way, the rapid diffusion of the defect passivation agent to the defect position of the perovskite film layer is facilitated, and the rapid repair of the defect is achieved.

[0014] In some embodiments of the present application, azobenzene is doped in the polymer matrix; and / or, zinc oxide piezoelectric nanowires are embedded in the polymer matrix. Azobenzene can undergo cis-trans isomerization under the irradiation of light of a specific wavelength, causing the shrinkage or expansion of the polymer matrix, promoting the release of the defect passivation agent, and thus facilitating the repair of the defect.

[0015] In some embodiments of the present application, the mass content of azobenzene is 0.1-2% based on the total mass of the polymer matrix.

[0016] In some embodiments of the present application, the diameter of the zinc oxide piezoelectric nanowires is 10-50 nm.

[0017] In some embodiments of the present application, the mass content of the zinc oxide piezoelectric nanowires is 1-10% based on the total mass of the repairing layer.

[0018] In another aspect of the present application, the present application provides a perovskite solar cell. In some embodiments of the present application, the perovskite solar cell comprises a perovskite light-absorbing layer and the repairing layer described above, and the repairing layer is located on at least part of the surface of the perovskite light-absorbing layer. In this way, the perovskite solar cell has all the features and advantages of the repairing layer described above, which will not be repeated here. In general, the perovskite solar cell has good stability and a long service life.

[0019] In yet another aspect of the present application, the present application provides a tandem cell. In some embodiments of the present application, the tandem cell comprises the repairing layer described above, or the tandem cell comprises the perovskite solar cell described above. In this way, the tandem cell has all the features and advantages of the repairing layer or the perovskite solar cell described above, which will not be repeated here.

[0020] In yet another aspect of the present application, a photovoltaic module is provided. In some embodiments of the present application, the photovoltaic module comprises the perovskite solar cell as described above, or the photovoltaic module comprises the tandem cell as described above. Thus, the photovoltaic module has all the features and advantages of the perovskite solar cell or the photovoltaic module as described above, which will not be repeated here. BRIEF DESCRIPTION OF DRAWINGS

[0021] The above and / or additional aspects and advantages of the present application will become apparent and be readily appreciated from the following description, including the appended drawings, wherein: Figure 1 A schematic diagram of a structure of a perovskite solar cell according to an embodiment of the present application is shown; Figure 2 A schematic diagram of a structure of a tandem cell according to an embodiment of the present application is shown.

[0022] REFERENCE SIGNS: 11: conductive substrate; 12: first transport layer; 13: perovskite light-absorbing layer; 14: repair layer; 15: second transport layer; 16: first electrode; 10: top cell; 20: bottom cell; 2: connecting layer. DETAILED DESCRIPTION

[0023] Embodiments of the present application are described in detail below with reference to examples illustrated in the accompanying drawings, in which the same or similar components have the same or similar designations throughout, and in which: the embodiments described below are exemplary only, and are not intended to be limiting of the present application.

[0024] The present application aims to overcome the shortcomings of the prior art, and to provide a repair layer that can solve at least one of the following core problems: Physical-chemical repair split problem: the prior art cannot simultaneously repair physical cracks caused by mechanical stress and chemical defects (such as iodine vacancies) caused by a humid and hot environment.

[0025] Repair response delay problem: traditional repair methods (such as immersion in a passivation agent solution) have a slow response, and cannot intervene in time at the initial stage of damage, leading to irreversible performance degradation.

[0026] High-temperature repair failure problem: the dynamic chemical bond network of traditional self-repairing polymers is easily disintegrated at an environment above 60°C, and cannot meet the stability requirements at the actual working temperature of solar cells.

[0027] In one aspect of this application, a repair layer is proposed. In some embodiments of this application, the repair layer comprises a polymer matrix and a composite dispersed within the polymer matrix. The polymer matrix contains one or more of the following: hydroxyl (-OH), primary amine (-NH2), secondary amine (-NH-), dynamic borate ester bonds, disulfide bonds (-SS-), Diels-Alder rings, imine bonds, and supramolecular polymers. The composite comprises a porous support and a defect passivating agent. The porous support loads the defect passivating agent, which includes one or more of the following: hydrocarbon ammonium iodide salts, sulfur-containing passivating agents, purine alkaloids, organophosphorus oxides, guanidine salts, and chelating passivating agents. The purine alkaloids contain carbonyl groups. This repair layer can intelligently sense changes in the surrounding environment (temperature and humidity) and trigger two independent but synergistic repair mechanisms.

[0028] Hydroxyl groups, primary amine groups, and secondary amine groups in the polymer matrix can form hydrogen bonds. Hydrogen bonds are highly sensitive to moisture. When the ambient humidity increases, water molecules, acting as plasticizers, can promote the breaking and recombination of hydrogen bonds, thereby repairing physical cracks and healing them.

[0029] Dynamic borate ester bonds are dynamic bonds composed of boric acid groups and ligands such as hydroxyl, aryl, and alkyl groups. They can break and recombine under certain conditions. Dynamic borate ester bonds are temperature-sensitive and can undergo reversible transesterification reactions at elevated temperatures (e.g., temperatures > 50°C), endowing the polymer matrix (network structure) with fluidity and reconfiguration capabilities at high temperatures, thus repairing defects.

[0030] The thermal exchange reaction of disulfide bonds can be used as a temperature response mechanism to repair defects: under heating conditions, disulfide bonds can undergo reversible breakage and recombination, enabling the polymer matrix to achieve dynamic behaviors such as stress relaxation, self-repair, and reprocessability, which is beneficial for repairing defects in perovskite films.

[0031] The Diels-Alder reaction, also known as diene synthesis, refers to the cycloaddition process between a conjugated diene (i.e., a diene) and an alkene or alkyne containing one or more carbon-carbon double bonds (i.e., a dienophile). The resulting cyclic structure is called a Diels-Alder ring. The Diels-Alder ring is a thermally reversible structure. At higher temperatures (e.g., 110℃-150℃), the reverse reaction occurs, generating the starting materials (diene and dienophile). At lower temperatures (e.g., 55℃-80℃), the cycloaddition reaction occurs, forming the Diels-Alder ring structure. Therefore, polymer matrices containing Diels-Alder rings can also respond to temperature changes, promoting the repair of defects in perovskite films.

[0032] Imine bonds (containing carbon-nitrogen double bonds) are dynamically reversible in the presence of water, enabling humidity response.

[0033] Supramolecular polymers are high-molecular aggregates formed by the reversible non-covalent self-assembly of small molecules or repeating units through hydrogen bonding, π-π stacking, host-guest interactions, etc., exhibiting dynamic reversibility. Supramolecular polymers are highly sensitive to changes in temperature and humidity (water molecules), and can respond to changes in humidity and temperature to promote defect repair.

[0034] In some embodiments, the polymer matrix comprises a polyacrylamide-polyethylene glycol hydrogel. This matrix can form abundant hydrogen bonds and is responsive to changes in humidity.

[0035] In some embodiments, the polymer matrix comprises a polyacrylamide-polyethylene glycol (PAAm-PEG) hydrogel containing dynamic borate ester bonds. The PAAm-PEG hydrogel has an interpenetrating network structure; the PAAm network provides mechanical strength and toughness, while the PEG network provides flexibility. The combination of these two structures makes the entire hydrogel a matrix possessing both flexibility and mechanical strength, enabling good physical contact with the perovskite film. In this system, the two network structures can undertake different repair tasks. The amide groups in the PAAm network can form humidity-sensitive hydrogen bonds, and similarly, the hydroxyl groups in the PEG network can also form hydrogen bonds. These hydrogen bonds are highly sensitive to humidity; when ambient humidity increases, water molecules can promote the breaking and recombination of hydrogen bonds, thereby repairing physical cracks in the perovskite film. The PEG network contains abundant hydroxyl groups, which can form temperature-sensitive dynamic borate ester bonds with borate groups, responding to temperature changes. This matrix network structure, containing both hydrogen bonds and dynamic borate ester bonds, enables a synergistic repair mechanism triggered by both humidity (hydrogen bonds) and heat (dynamic borate ester bonds), promoting defect repair in the perovskite film.

[0036] In some embodiments, to introduce dynamic borate ester bonds into a polyacrylamide (PAAm) network, a molecule containing both a "boronic acid group" and a "polymerizable functional group (such as vinyl group)" (a crosslinking functional monomer) can be copolymerized with acrylamide monomers. For example, during preparation, 4-vinylphenylboronic acid (4-VPBA) can be added to the reaction system as a functional monomer to copolymerize with acrylamide monomers, thereby binding the borate group to the PAAm polymer chain and polymerizing it into the network backbone via covalent bonds. 4-Vinylphenylboronic acid participates in the formation of the polyacrylamide network as one of the reactive monomers, its vinyl (CH2=CH-) portion opening and linking with the acrylamide molecule to become part of the PAAm backbone. Thus, the phenylboronic acid group at its other end is bound to the polymer backbone as a side group. Subsequently, these borate groups bound to the PAAm chain form dynamic borate ester bonds across the network with the hydroxyl groups on the PEG chains running through the network. In other embodiments, other similar vinylboronic acid derivatives can be used to copolymerize with acrylamide monomers.

[0037] In some embodiments, a solvent (e.g., water), acrylamide, a functional monomer (e.g., 4-VPBA), polyethylene glycol, and an initiator (e.g., a photoinitiator) can be mixed to form a prepolymer solution. The prepolymer solution is then mixed with a composite to obtain a mixed solution. This mixed solution is then subjected to steps such as coating, imprinting, and curing to form a repair layer. In some embodiments, the initiator may include commonly used initiators such as Irgacure 2959. The specific amount of initiator is not particularly limited in this application; those skilled in the art can set and adjust it as needed, as long as it can initiate the polymerization reaction.

[0038] In some embodiments of this application, the amount of functional monomer (e.g., 4-VPBA) used as a crosslinking agent can be much lower than that of the main monomer (acrylamide), and the molar ratio is typically between 1% and 10%. For example, the molar ratio of 4-VPBA to acrylamide can be 1:100, 1:50, 3:100, 1:20, 7:100, 1:10, etc. If the amount of functional monomer is too low, it may result in insufficient crosslinking point density, making it impossible to form an effective temperature-controlled dynamic network, and resulting in poor flowability and reconstruction ability at high temperatures. If the amount of functional monomer is too high, it may make the polymer network too rigid, increasing the brittleness of the polyacrylamide-polyethylene glycol hydrogel and affecting its basic mechanical properties as a flexible repair layer. It may also affect the reversible exchange efficiency of dynamic borate ester bonds due to steric hindrance.

[0039] In some embodiments, the polymer matrix includes a polyurethane elastomer, which has excellent mechanical properties and can improve the flexibility of the repair layer. When used in flexible batteries, it can reduce the bending radius of the battery. The main chain of the polyurethane elastomer contains urethane groups and has many hydrogen bonds, which can achieve humidity response and play a role in repairing defects in the perovskite film.

[0040] In some embodiments, the polymer matrix may include a polyvinyl alcohol-based hydrogel. This matrix can form abundant hydrogen bonds and respond to changes in humidity.

[0041] In some embodiments, the polymer matrix may include a polyvinyl alcohol-based hydrogel containing dynamic borate ester bonds. The abundant hydroxyl groups of polyvinyl alcohol can be used to form a humidity-sensitive hydrogen bond network, and a temperature response can be achieved by introducing other dynamic bonds, such as dynamic borate ester bonds. In some embodiments, 4-vinylphenylboronic acid or other similar vinylboronic acid derivatives may be added to the reaction system during the preparation of the polyvinyl alcohol-based hydrogel.

[0042] In some embodiments, the polymer matrix may include chitosan and / or alginate. The aforementioned matrix can form abundant hydrogen bonds, enabling a response to humidity.

[0043] In some embodiments, the polymer matrix may include chitosan and / or alginate, and contains dynamic borate ester bonds. Chitosan and alginate are naturally rich in functional groups that can form hydrogen bonds, enabling humidity-responsive functionality, and temperature-responsive mechanisms can be introduced through chemical modification, for example, by modifying chitosan or alginate with 4-vinylphenylboronic acid or other similar vinylboronic acid derivatives to introduce dynamic borate ester bonds into the molecular chain.

[0044] In some embodiments, the polymer matrix may include polyurea or polyurethane and contain disulfide bonds. A temperature-responsive mechanism is achieved through the heat exchange reaction of disulfide bonds, while hydrogen-bonding groups (such as urea groups) are designed into the polymer backbone to respond to humidity. Typical monomers for synthesizing the above polymer matrix include isocyanate monomers and amine / alcohol monomers. Additionally, disulfide bonds can be introduced into the polymer network using a dynamic crosslinking agent containing disulfide bonds. Isocyanate monomers form the "hard segment" portion of the polyurea / polyurethane backbone, and the urea groups (-NH-CO-NH-) they form are the main contributors to hydrogen bonding. In some embodiments, the isocyanate monomer may be selected from at least one of isophorone diisocyanate (IPDI) and hexamethylene diisocyanate (HDI). Amine / alcohol monomers form the "soft segment" portion of the backbone, determining the material's flexibility and elasticity. In some embodiments, the amine / alcohol monomer may be selected from at least one of polyetheramine and polytetrahydrofuran glycol. Dynamic crosslinking agents are functional molecules that enable temperature-responsive behavior. For example, bis(4-aminophenyl) disulfide, containing two amino groups, can react with isocyanate monomers to introduce reversible disulfide bonds (-SS-) as crosslinking points into the polymer network, providing temperature responsiveness. In some specific embodiments, IPDI can be reacted with polyetheramine, with a stoichiometric amount of bis(4-aminophenyl) disulfide added simultaneously, to prepare a self-healing elastomer with dual responsive functions via a one-step polymerization method.

[0045] In some embodiments, the polymer matrix may contain Diels-Alder rings and imine bonds. This system can be achieved by constructing two interwoven networks, each crosslinked by different dynamic bonds. Exemplarily, one network is a Diels-Alder temperature-controlled network containing Diels-Alder rings, with raw materials including furan-containing monomers or polymers (e.g., furfuryl methacrylate (FMA), which can introduce furan rings via free radical polymerization) and maleimide-containing crosslinking agents (e.g., 1,1'-(methylenedi-4,1-phenylene)bismaleimide, a bifunctional crosslinking agent capable of undergoing a DA reaction (Diels-Alder reaction) with both furan rings to form stable, thermally reversible crosslinking points). The other network is a Schiff base / imine bond humidity-sensitive network, obtained by reacting an aldehyde-containing polymer with an amine-containing polymer. The aldehyde-containing polymer can be selected from at least one of oxidized sodium alginate and oxidized dextran, and can be introduced into the molecular chain of natural polysaccharides by treating them with an oxidizing agent such as sodium periodate to introduce a large number of aldehyde groups. The amine-containing polymer can be selected from at least one of chitosan (a natural polysaccharide with a large number of primary amine groups on its molecular chain) and polyethyleneimine (PEI, a synthetic polymer containing a large number of primary, secondary, and tertiary amine groups).

[0046] In some specific embodiments, a polymer matrix containing Diels-Alder rings and imine bonds can be prepared by the following method: First, furfuryl methacrylate (FMA) is polymerized to obtain polymer chains with numerous furan side groups. Then, the above polymer is mixed with 1,1'-(methylenedi-4,1-phenylene)bismaleimide, and a first thermoreversible network is formed through a DA reaction. Next, sodium alginate oxide and chitosan are introduced into this network. The aldehyde groups on sodium alginate oxide react in situ with the amino groups on chitosan to form dynamically reversible Schiff base / imine bonds, constituting a second humidity-sensitive network. Using the above method, a sophisticated polymer material integrating two types of dynamic chemical bonds that respond to temperature and humidity respectively can be obtained.

[0047] In some embodiments, the polymer matrix may include a supramolecular polymer containing a cyclodextrin host and an adamantane guest. The interaction between the cyclodextrin host and the adamantane guest is utilized to form a dynamic cross-linked network; this interaction is sensitive to changes in temperature and water molecules, enabling temperature- and humidity-responsive functionality.

[0048] In this application, a composite is dispersed in the polymer matrix. The composite includes a porous support and a defect passivating agent. Under certain conditions (such as heating conditions), the pore size of the porous support will expand and the defect passivating agent will be released to repair defects in the perovskite film.

[0049] In some embodiments of this application, the mass content of the composite can be 5%-25% based on the total mass of the repair layer. For example, the mass content of the composite can be 5%, 8%, 10%, 12%, 15%, 17%, 20%, 23%, 25%, etc. A composite content within the above range can balance repair efficiency and the quality of the repair layer film. If the mass content of the composite is less than 5%, it may lead to insufficient defect passivating agent reserves, making it difficult to continuously and effectively repair chemical defects in the perovskite film throughout the device's lifespan. If the mass content of the composite is greater than 25%, excessive composite nanoparticles may aggregate in the polymer matrix (e.g., hydrogel matrix), affecting the mechanical properties and optical transparency of the repair layer, and may also hinder the healing process of physical cracks. In some specific embodiments, the mass content of the composite can be 15% based on the total mass of the repair layer, thereby achieving an optimal balance between repair efficiency and film quality.

[0050] In some embodiments, the mass of the defect passivating agent in the composite can be 5%-20% of the mass of the porous support. For example, the mass of the defect passivating agent can be 5%, 8%, 10%, 12%, 16%, 18%, 20%, etc., of the porous support. Therefore, the defect passivating agent can, to a certain extent, repair chemical defects.

[0051] In some embodiments, the mass of the defect passivating agent in the composite can be 15%-20% of the mass of the porous carrier. Thus, when the content of the defect passivating agent is within a suitable range, chemical defects in the perovskite film can be effectively passivated.

[0052] In some embodiments, the porous support may include one or more of zeolite imidazole ester frameworks (e.g., ZIF-8) and mesoporous silica. The aforementioned porous support has a porous structure and can be used as a carrier for defect passivating agents, releasing the passivating agent under certain conditions.

[0053] Zeolite imidazole ester frameworks possess regular channels and excellent thermal stability, making them suitable for storing and transporting defect passivators. These porous supports can load approximately 15% of their mass as defect passivators. The pores of the zeolite imidazole ester framework undergo structural relaxation upon temperature increase, leading to pore size expansion and triggering the controlled release of the internal defect passivator. Its release kinetics conform to the following formula, ensuring precise and on-demand release at high temperatures:

[0054] Where C is the release concentration, t is the time, R is the ideal gas constant (8.314 J / mol·K), and T is the absolute temperature (in K).

[0055] Mesoporous silica has a porous structure that can support approximately 20% of its mass as a defect passivating agent.

[0056] The defect passivating agent in this application may include one or more of the following: hydrocarbon ammonium iodide salts, sulfur-containing passivating agents, purine alkaloids, organophosphorus oxides, guanidine salts, and chelating passivating agents. The above-mentioned defect passivating agents repair at least one of iodine vacancies, lead ion defects, and organic cation defects in perovskite films. The following is a detailed description of different types of defect passivating agents.

[0057] Hydrocarbon-based ammonium iodides can form strong interactions with iodine vacancies, repairing chemical defects at these vacancies and effectively inhibiting non-radiative recombination. In some embodiments, the hydrocarbon-based ammonium iodide may include hexylammonium iodide (C6H4O2). 15 One or more of ni (ni) and phenylethyl ammonium iodide (PEAI). Hexyl ammonium iodide can form a strong interaction with iodine vacancies (binding energy calculated by DFT is -2.3 eV), effectively suppressing nonradiative recombination. Compared with hexyl ammonium iodide, phenylethyl ammonium iodide has a stronger passivation effect, and its binding energy with defects can be increased to -2.5 eV, but the synthesis cost will increase by about 30%.

[0058] Sulfur-containing passivating agents contain electron-rich sulfur atoms, which can react with electron-deficient Pb atoms. 2+Coordination bonds are formed, thereby reducing defects. In some embodiments, sulfur-containing passivating agents include one or more of thiourea and L-cysteine. The sulfur atoms in the thiourea molecule can effectively passivate Pb. 2+ The drawback is that L-cysteine ​​contains a thiol group, which can also strongly coordinate with lead ions.

[0059] Purine alkaloids are a class of alkaloids containing a purine core or its derivatives, whose basic skeleton is an aromatic heterocyclic structure formed by the fusion of imidazole and pyrimidine. The purine alkaloids in this application contain a carbonyl group in their molecular structure, which can serve as a Lewis base site for binding with Pb. 2+ Coordination, passivating lead ion defects. In some embodiments, purine alkaloids include one or more of caffeine, theophylline, and theobromine.

[0060] Organophosphorus oxides contain phosphine oxide groups, and the oxygen atoms in these groups have strong coordinating abilities, which can effectively passivate Pb. 2+ Defects. In some embodiments, the organophosphorus oxide may include one or more of trioctylphosphine oxide, triethylphosphine oxide, and tributylphosphine oxide.

[0061] The size and hydrogen bonding ability of guanidine salts (such as guanidine iodide) can help stabilize the perovskite lattice and repair methylamine ions (MA). + Defects such as vacancies. In some embodiments, the guanidine salt may include guanidine iodide.

[0062] Chelating passivating agents typically possess multiple coordination sites, enabling them to bind metal ions and form stable structures, thereby passivating metal ion defects in perovskite films. In some embodiments, chelating passivating agents may include one or more of ethylenediaminetetraacetic acid (EDTA) and crown ethers. EDTA and its derivatives can effectively passivate lead defects and inhibit ion migration. The cyclic structure of crown ethers can interact simultaneously with both organic cations and inorganic lead ions, playing a dual role in stabilizing the crystal lattice and passivating the surface.

[0063] In some embodiments, the polymer matrix is ​​a hydrogel matrix, specifically a PAAm-PEG interpenetrating network hydrogel, which provides mechanical flexibility and an elongation at break of up to 380%, ensuring good contact with the perovskite film. Dynamic borate ester bonds and hydrogen bonds are introduced into the hydrogel network, creating a dual triggering mechanism that is synergistically activated under 60°C and 70%RH conditions to achieve physical repair. The composite uses ZIF-8 supported hexylammonium iodide (C6H4O2). 15 NI), a temperature-controlled release defect passivating agent, with hexyl ammonium iodide accounting for 15% of the mass of ZIF-8. Hexyl ammonium iodide has a thermal decomposition temperature >300℃ and exhibits good thermal stability.

[0064] In some embodiments of this application, the thickness of the repair layer can be 20nm-50nm, for example, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, etc. Thus, within a suitable thickness range, the repair layer can repair physical cracks in the perovskite film, and can support a large number of composite particles, promoting the repair of chemical defects in the perovskite film, thereby achieving a better repair effect. If the repair layer is too thin, the total amount of composite particles it can support may be insufficient, affecting the durability of chemical repair. Simultaneously, an excessively thin polymer matrix is ​​also difficult to effectively repair physical cracks. Conversely, if the repair layer is too thick, the repair layer itself may become a significant obstacle to charge transport, increasing the hole transport resistance from the perovskite film to the hole transport layer (e.g., the Spiro-OMeTAD layer), leading to a reduction in the device's fill factor (FF) and overall efficiency.

[0065] In some embodiments of this application, the repair layer may include multiple microchannels extending along the thickness direction. Thus, the microchannels can form a rapid transport path, allowing the defect passivating agent to rapidly diffuse along the microchannels to any damaged location in the perovskite film after release from the porous carrier, achieving rapid repair of chemical defects. In some embodiments, the microchannels are parallel to the thickness direction of the repair layer.

[0066] In some embodiments, the pore size of the microchannel is 50nm-100nm, for example, the pore size of the microchannel can be 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, etc. This facilitates the rapid transport of the defect passivating agent, enabling rapid repair of chemical defects, and also allows the repair layer to maintain good structural integrity, making it less prone to stress concentration points. The 50nm-100nm microchannel size represents an optimal balance between ensuring rapid transport, avoiding clogging, maintaining the mechanical properties of the repair layer, and not affecting the electrical performance of the device.

[0067] If the pore size of the microchannel is too small, it may reduce the transport efficiency of the defect passivator. An overly narrow microchannel will significantly increase the resistance to diffusion of defect passivator molecules (wall effect), and may not be able to achieve the effect of rapid repair within 10 seconds. In addition, microchannels are prone to clogging. The released defect passivator molecules may aggregate in the channel or be blocked by impurities or polymer segments that may exist in the polymer matrix network, causing partial or even complete failure of the transport network. Furthermore, the fabrication of microchannels with too small a pore size is more difficult. In nanoimprinting, the fabrication of smaller channels requires higher requirements for molds and process control, which will increase manufacturing costs and the defect rate.

[0068] If the pore size of the microchannel is too large, it may damage the mechanical properties of the repair layer. The repair layer itself also undertakes the function of physical repair. Excessively large pores will severely weaken the mechanical integrity of the polymer matrix. When physical cracks occur, the excessively large microchannels themselves will become stress concentration points, which may accelerate crack propagation and lead to a decrease in repair capability. It will also affect the electrical performance of the device. The repair layer is located between the perovskite light-absorbing layer and the hole transport layer (or electron transport layer). Excessively large microchannels mean that there are pores between these two key layers, which may lead to poor local contact, affecting the effective extraction of charge carriers (holes or electrons), thereby reducing the fill factor (FF) and photoelectric conversion efficiency of the battery. In addition, it may interfere with the deposition of the top film. For example, when spin-coating the hole transport layer (Spiro-OMeTAD layer) on the repair layer, excessively large pores may cause solution penetration or uneven film formation, thereby affecting the overall performance and stability of the device.

[0069] In some embodiments of this application, the cross-section of the microchannel perpendicular to the thickness direction of the repair layer can be circular, elliptical, rectangular, polygonal (e.g., triangular, rectangular, hexagonal, etc.), or irregular in shape. The repair layer has multiple microchannels, and the cross-sectional shapes of the multiple microchannels perpendicular to the thickness direction of the repair layer can be the same or different.

[0070] It should be noted that, in this application, the aperture of a microchannel refers to the maximum distance between any two points on the cross-section of the microchannel along the thickness direction of the repair layer. When the cross-section of the microchannel perpendicular to the thickness direction of the repair layer is circular, the aperture of the microchannel refers to the diameter of the circle; when the cross-section of the microchannel perpendicular to the thickness direction of the repair layer is rectangular, the aperture of the microchannel refers to the length of the diagonal of the rectangle.

[0071] In some embodiments of this application, the spacing between the centers of two adjacent microchannels can be 200nm-500nm, for example, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, 500nm, etc. This ensures that the repair layer has sufficient mechanical strength to heal physical cracks (avoiding structural weakening due to excessive spacing), and also ensures that any defect passivating agent released at any location within the layer can enter the high-speed transmission network quickly enough (avoiding reduced response speed due to excessive spacing). It should be noted that the center of the microchannel refers to the geometric center of the cross-section of the microchannel along the thickness direction of the repair layer.

[0072] In some embodiments of this application, a PDMS mold with arrayed nanopillars can be used to imprint the repair layer, forming multiple microchannels. The size and shape of the nanopillars are substantially consistent with the size and shape of the microchannels. It is understood that the diameter, shape, and height of the protruding nanopillars on the PDMS mold directly determine the diameter, shape, and depth of the recessed microchannels formed on the repair layer after imprinting. The spacing between the nanopillars is adjustable; the spacing of the nanopillars on the mold is a key design parameter that can be adjusted according to requirements, and it determines the distribution density of the microchannels.

[0073] In some embodiments of this application, the polymer matrix may be doped with azobenzene, which is a photoresponsive material. Under visible light with a wavelength of 405 nm, it undergoes a cis-trans isomerization transition, causing the polymer matrix network to shrink or expand, thereby triggering the release of the defect passivator. The response time can be shortened to less than 5 seconds.

[0074] In some embodiments of this application, the mass content of azobenzene is 0.1%-2% based on the total mass of the polymer matrix. If the azobenzene content is too low, the mechanical deformation effect generated by the isomerization of azobenzene molecules under light is too weak to cause effective shrinkage or expansion of the polymer matrix network, resulting in low release efficiency of the defect passivator or failure of light triggering. If the azobenzene content is too high, excessive azobenzene molecules may aggregate in the polymer matrix network, affecting the optical transparency and film uniformity of the repair layer. In addition, high concentrations of dopant (azobenzene) may also adversely affect the mechanical properties and stability of the polymer matrix itself. In some embodiments, the mass content of azobenzene is 0.5% based on the total mass of the polymer matrix, which is an optimal addition concentration for balancing triggering efficiency and film material properties.

[0075] In some embodiments of this application, zinc oxide piezoelectric nanowires can be embedded in the polymer matrix. These zinc oxide piezoelectric nanowires can respond to changes in pressure; when the perovskite solar cell is bent or compressed, the ZnO piezoelectric nanowires in the repair layer generate a piezoelectric field that can trigger the release of a defect passivator encapsulated in an electric field-sensitive porous carrier.

[0076] In some embodiments, the diameter of the zinc oxide piezoelectric nanowires can be 10 nm to 50 nm. If the zinc oxide piezoelectric nanowires are too thin, the piezoelectric effect they produce may be weakened, insufficient to trigger the release of the defect passivating agent from the porous support. Furthermore, excessively thin nanowires are more prone to aggregation in the polymer matrix. If the diameter of the zinc oxide piezoelectric nanowires is too large, the thick nanowires may disrupt the network structure of the polymer matrix and the uniformity of the film, negatively impacting the mechanical and optical properties of the repair layer.

[0077] In some embodiments, the mass content of zinc oxide piezoelectric nanowires is 1%-10% based on the total mass of the repair layer; for example, the mass content of zinc oxide nanowires can be 1%, 3%, 5%, 8%, 10%, etc. If the amount of zinc oxide piezoelectric nanowires added is too low, the number of nanowires per unit volume will be insufficient, and even if the battery is subjected to bending, the total piezoelectric field strength generated may not reach the threshold for triggering the release of the porous carrier. ZnO piezoelectric nanowires are inorganic rigid materials; if the amount of zinc oxide piezoelectric nanowires added is too high, it may reduce the flexibility and self-healing ability of the polymer matrix. In addition, too many nanowires are also prone to agglomeration, leading to uneven electric field distribution and degraded device performance.

[0078] In another aspect of this application, a perovskite solar cell is proposed. In some embodiments of this application, reference is made to... Figure 1 The perovskite solar cell includes a perovskite light-absorbing layer 13 and the aforementioned repair layer 14, with the repair layer 14 located on at least a portion of the surface of the perovskite light-absorbing layer 13. Thus, the repair layer can repair physical and chemical defects in the perovskite light-absorbing layer, thereby improving the stability of the perovskite solar cell and extending its lifespan.

[0079] In some embodiments, reference Figure 1 The perovskite solar cell also includes a conductive substrate 11, a first transport layer 12, a second transport layer 15, and a first electrode 16. The first transport layer 12 is located between the conductive substrate 11 and the perovskite light-absorbing layer 13. The repair layer 14 is located on the side of the perovskite light-absorbing layer 13 away from the conductive substrate 11. The second transport layer 15 is located on the side of the repair layer 14 away from the perovskite light-absorbing layer 13. The first electrode 16 is located on the side of the second transport layer 15 away from the perovskite light-absorbing layer 13.

[0080] The conductive substrate 11 includes a substrate and a second electrode located on the substrate, the second electrode being disposed near the perovskite light-absorbing layer 13. In some embodiments, the substrate may be a glass substrate. In other embodiments, the substrate may be a flexible substrate, such as a PET (polyethylene terephthalate) substrate or a PEN (polyethylene naphthalate) substrate. In some embodiments, using a PET substrate or a PEN substrate, and employing a polyurethane elastomer as the polymer matrix in the repair layer, can reduce the bending radius of the battery to 2 mm while maintaining good repair function. In some embodiments, the second electrode may be a transparent conductive oxide electrode (e.g., ITO, FTO, IZO, etc.).

[0081] In some embodiments of this application, the first transport layer 12 can be an electron transport layer, and the second transport layer 15 can be a hole transport layer. In other embodiments of this application, the first transport layer 12 can be a hole transport layer, and the second transport layer 15 can be an electron transport layer.

[0082] In some embodiments, the material of the hole transport layer may include nickel oxide (NiO). x , 1≤x≤2), cuprous iodide (CuI), cuprous oxide (Cu2O), cuprous thiocyanate (CuSCN), 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (Spiro-OMeTAD), 2,2',7,7'-tetratetra(di-p-tolylamino)spiro-9,9'-difluorene (Spiro-TTB), poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), and [4-(3,6-dimethoxy-9H-carbazole-9-yl)butyl]phosphonic acid (MeO-4PACz), (4-(3,6-dimethyl ... (4-(9H-carbazole-9-yl)butyl)phosphonic acid (Me-4PACz), [4-(9H-carbazole-9-yl)butyl]phosphonic acid (4PACz), (4-(3,6-dibromo-9H-carbazole-9-yl)butyl)phosphonic acid (Br-4PACz), [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz), (2-(3,6-dimethyl-9H-carbazole-9-yl)ethyl)phosphonic acid (Me-2PACz), (2-(9H-carbazole-9-yl)ethyl)phosphonic acid (2PACz), (2-(3,6-dibromo-9H-carbazole-9-yl)ethyl)phosphonic acid (Br-2PACz), etc.

[0083] In some embodiments, the material of the electron transport layer may include, but is not limited to, tin oxide, fullerenes and their derivatives, imide compounds, quinone compounds, etc. Exemplarily, the imide compounds include one or more of phthalimide, succinimide, N-bromosuccinimide, glutarimide, or maleimide; exemplarily, the quinone compounds include one or more of benzoquinone, naphthoquinone, phenanthrenequinone, or anthraquinone; exemplarily, the fullerenes and their derivatives include fullerene C 60 Fullerene C 70 PCBM([6,6]-phenyl-C 61 methyl butyrate), [6,6]-phenyl C 71 Methyl butyrate (PC) 71 At least one of (BM). Further, the electron transport layer can be a single-layer structure, or a double-layer or triple-layer structure. In some specific embodiments, the electron transport layer can be a C layer with a thickness of 5-20 nm. 60 A layer of tin oxide with a thickness of 15-20 nm is added. The tin oxide layer can protect C in subsequent processes. 60 .

[0084] In some specific embodiments, the first transport layer 12 can be an electron transport layer, specifically a tin oxide layer, with a thickness of 20 to 40 nanometers. This ensures that the electron transport layer completely covers the second electrode of the conductive substrate to prevent short circuits and does not increase unnecessary series resistance. In some specific embodiments, the second transport layer 15 can be Spiro-OMeTAD, with a thickness of 150 to 250 nanometers. This layer can uniformly cover the underlying repair layer without significantly increasing cost or resistance.

[0085] In some embodiments of this application, the material of the perovskite light-absorbing layer 13 can be ABX3, wherein A is a monovalent cation, including but not limited to one or a mixture of several monovalent cations selected from cesium (Cs), rubidium (Rb), methylamino (CH3NH3), and formamidinyl (CH2(NH2)2); B is a divalent cation, including but not limited to one or a mixture of several divalent cations selected from lead (Pb) and tin (Sn); and X is a monovalent anion, including but not limited to one or a mixture of several monovalent anions selected from iodine (I), bromine (Br), chloride (Cl), fluorine (F), and thiocyanate (SCN). In some specific embodiments, the material of the perovskite light-absorbing layer 13 can be Cs. x FA 1-x Pb(I y Br 1-y 3, x and y are 0 and 1 respectively.

[0086] In some embodiments of this application, the thickness of the perovskite light-absorbing layer 13 can be 400 to 600 nanometers. For example, the thickness of the perovskite light-absorbing layer 13 can be 400 nanometers, 450 nanometers, 500 nanometers, 550 nanometers, 600 nanometers, etc., which is beneficial for fully absorbing light.

[0087] In some specific embodiments, the perovskite light-absorbing layer 13 can be made of CH3NH3PbI3 and has a thickness of 500 nanometers.

[0088] In some embodiments of this application, the first electrode 16 can be a silver electrode with a thickness of 80 to 150 nanometers. This provides the electrode with good conductivity while avoiding increased material costs and mechanical stress due to excessive electrode thickness.

[0089] Compared with perovskite solar cells without a repair layer, the technical solution of this application has the following significant advantages: (1) Breakthrough in synergistic repair efficiency: It can achieve simultaneous repair of physical and chemical damage. (2) Significantly improved device stability. (3) Fast response and cost advantage: Thanks to the nano-microchannel design, the response time for defect passivator transport does not exceed 10 seconds. In addition, the materials used (PAAm, PEG, ZIF-8, etc.) are inexpensive. According to calculations, the total material cost of the battery increases by less than 3% after the introduction of this repair layer. Considering the benefits brought by the extended lifespan, the unit power cost is reduced by 20% (calculated based on a 5-year lifespan).

[0090] In another aspect of this application, a tandem solar cell is proposed. In some embodiments of this application, the tandem solar cell includes the aforementioned repair layer, or the tandem solar cell includes the aforementioned perovskite solar cell.

[0091] In some embodiments of this application, reference is made to Figure 2 The tandem solar cell includes a top cell 10 and a bottom cell 20, wherein the top cell 10 can be a perovskite solar cell, and the bottom cell 20 is located on the back side of the perovskite solar cell. In some embodiments, the bottom cell 20 can be a crystalline silicon cell.

[0092] In some embodiments of this application, a connecting layer 2 may be provided between the top cell 10 and the bottom cell 20. The connecting layer 2 may include at least one of a transparent conductive oxide layer (TCO layer), a doped polycrystalline silicon layer, etc., without particular limitation in this application. Specifically, the TCO layer may be indium tin oxide, aluminum-doped zinc oxide, fluorine-doped tin oxide, antimony-doped tin oxide, indium-doped zinc oxide, etc.; the doped polycrystalline silicon layer may be P-type doped polycrystalline silicon (e.g., boron-doped polycrystalline silicon) or N-type doped polycrystalline silicon (e.g., phosphorus-doped polycrystalline silicon). The films made of the above materials have good conductivity, which is beneficial for improving the carrier transport and collection capabilities of the tandem solar cell. In some specific embodiments of this application, the connecting layer 2 may be an ITO layer or an FTO layer.

[0093] In this application, the repair layer can be used in perovskite / silicon heterojunction tandem solar cells. It can not only repair the damage of the top perovskite cell, but also improve the interface energy level matching and mechanical contact between the two cells, which can further improve the efficiency of the tandem solar cells.

[0094] In another aspect of this application, a photovoltaic module is proposed. In some embodiments of this application, the photovoltaic module includes the perovskite solar cell described above, or the photovoltaic module includes the tandem cell described above.

[0095] In some embodiments of this application, the photovoltaic module may include one or more perovskite solar cells, or the photovoltaic module may include one or more tandem cells.

[0096] The present application will be described below through specific embodiments. Those skilled in the art will understand that the specific embodiments below are merely illustrative and do not limit the scope of the present application in any way. Furthermore, in the following embodiments, unless otherwise specified, the materials and equipment used are commercially available. If specific processing conditions and methods are not explicitly described in the later embodiments, conditions and methods known in the art can be used for processing.

[0097] Example 1 Perovskite solar cell design: The structure employs a nip upright planar structure, with the following stacking order: glass / ITO / SnO2 (25nm thick) / CH3NH3PbI3 (500nm thick) / repair layer (30nm thick) / Spiro-OMeTAD (200nm thick) / Ag (100nm thick). The repair layer contains microchannels with an average diameter of 80nm formed using nanoimprint lithography.

[0098] Fabrication process of perovskite solar cells: 1. Preparation of substrate and electron transport layer: Clean the ITO conductive glass, spin-coat an alcohol solution of SnO2 nanoparticles, anneal, and form an electron transport layer.

[0099] 2. Preparation of perovskite light-absorbing layer: A CH3NH3PbI3 perovskite precursor solution was deposited on the SnO2 layer by a one-step spin coating method, followed by annealing to form a perovskite light-absorbing layer with a thickness of approximately 500 nm.

[0100] 3. Preparation of the repair layer: a. Synthesis of prepolymer solution: Solvent water, acrylamide (main monomer), 4-vinylphenylboronic acid (functional monomer, the molar ratio of 4-vinylphenylboronic acid to acrylamide is 3:100), polyethylene glycol (PEG, CAS No. 25322-68-3) and photoinitiator are mixed to form a homogeneous prepolymer solution.

[0101] b. Preparation and spraying of the composite and prepolymer mixed solution: ZIF-8@C6H 15 NI nanoparticles (ZIF-8 loaded with C6H) 15 NI, where C6H 15Ni (15% of the mass of ZIF-8) is dispersed in the above prepolymer solution to form a mixed solution with a total solid content of 20%. Then, this mixed solution is uniformly coated onto the surface of the perovskite light-absorbing layer using an ultrasonic spraying method.

[0102] c. Imprinting and curing: Imprinting was performed using a PDMS mold with an array of nanopillars, simultaneously at 365 nm and 15 mW / cm². 2 The material is cured under ultraviolet light for 30 seconds to form a repair layer with microchannels. Based on the total mass of the repair layer, ZIF-8@C6H 15 The mass content of NI nanoparticles is 15%.

[0103] 4. Hole transport layer and electrode fabrication: Spiro-OMeTAD was spin-coated on top of the repair layer as a hole transport layer. Finally, a 100 nm thick Ag electrode was deposited by vacuum thermal evaporation.

[0104] Comparative Example 1 Unlike Example 1, the perovskite solar cell in Comparative Example 1 does not have a repair layer.

[0105] The efficiency data of the solar cells in Test Example 1 and Comparative Example 1 under different conditions are retained. The test conditions and test results are recorded in Table 1.

[0106] Table 1 Battery stability test conditions and test results

[0107] As can be seen from Table 1, compared with Comparative Example 1, the battery in Example 1 has a higher efficiency retention rate after being placed under humid and hot conditions for a long time, or after undergoing multiple cycles of low temperature and high temperature. The battery in Example 1 has better stability.

[0108] Example 2 Unlike Example 1, the glass substrate in the ITO conductive glass is replaced with a PET substrate.

[0109] The repair efficiency of the solar cell in Example 2 for different defects, the test conditions and test results are recorded in Table 2.

[0110] Table 2. Repair efficiency of solar cells for different defects and test conditions in Example 2.

[0111] The sources and testing methods for physical cracks are shown in Table 2: (1) Applying mechanical stress: Apply mechanical stress to the prepared flexible battery through bending tests. For example, repeatedly bending it or bending it on a cylinder of a specific radius will induce microcracks in perovskite, a brittle ionic crystal material.

[0112] (2) Positioning and measurement: After stress is applied, the surface of the perovskite light-absorbing layer is observed using a microscope (such as an optical microscope or a scanning electron microscope) to find a physical crack with a width of about 10 μm as the test object.

[0113] (3) Conduct repair tests: Place the battery with a clearly sized crack under the test conditions described in Table 2 (60°C / 70% RH environment), observe and record its healing process and repair efficiency.

[0114] As can be seen from the test data in Table 2, the repair layer in Example 2 can effectively repair the physical cracks and chemical defects in the perovskite light-absorbing layer.

[0115] In the description of this application, the terms "front", "back", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are used only for the convenience of describing this application and do not require this application to be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this application.

[0116] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," and "other embodiments" indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment is included in at least one embodiment of this application. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples, without contradiction. Additionally, it should be noted that in this specification, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features.

[0117] Although embodiments of this application have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting this application. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of this application.

Claims

1. A repair layer, characterized in that, The invention comprises a polymer matrix and a composite dispersed in the polymer matrix. The polymer matrix contains one or more of the following: hydroxyl groups, primary amine groups, secondary amine groups, dynamic borate ester bonds, disulfide bonds, Diels-Alder rings, imine bonds, and supramolecular polymers. The composite comprises a porous support and a defect passivating agent. The porous support supports the defect passivating agent. The defect passivating agent comprises one or more of the following: hydrocarbon ammonium iodide salts, sulfur-containing passivating agents, purine alkaloids, organophosphorus oxides, guanidine salts, and chelating passivating agents. The purine alkaloids contain carbonyl groups.

2. The repair layer according to claim 1, characterized in that, The polymer matrix satisfies one of the following conditions: The polymer matrix comprises polyacrylamide-polyethylene glycol hydrogel and contains dynamic borate ester bonds; The polymer matrix includes a polyurethane elastomer; The polymer matrix comprises a polyvinyl alcohol-based hydrogel and contains dynamic borate ester bonds; The polymer matrix comprises chitosan and / or alginate, and contains dynamic borate ester bonds; The polymer matrix includes polyurea or polyurethane and contains disulfide bonds; The polymer matrix contains Diels-Alder rings and imine bonds; The polymer matrix includes a supramolecular polymer containing a cyclodextrin host and an adamantane guest.

3. The repair layer according to claim 1, characterized in that, The defect passivating agent satisfies at least one of the following conditions: The hydrocarbon ammonium iodide salt includes one or more of hexylammonium iodide and phenethylammonium iodide; The sulfur-containing passivating agent includes one or more of thiourea and L-cysteine; The purine alkaloids include one or more of caffeine, theophylline, and theobromine; The organophosphorus oxides include one or more of trioctylphosphine oxide, triethylphosphine oxide, and tributylphosphine oxide; The guanidine salt includes guanidine iodide; The chelating passivating agent includes one or more of ethylenediaminetetraacetic acid and crown ether.

4. The repair layer according to claim 1, characterized in that, The porous support includes one or more of zeolite imidazole ester framework and mesoporous silica.

5. The repair layer according to claim 1, characterized in that, The repair layer satisfies at least one of the following conditions: The thickness of the repair layer is 20nm-50nm; The repair layer includes multiple microchannels extending along the thickness direction; Based on the total mass of the repair layer, the mass content of the composite is 5%-25%.

6. The repair layer according to claim 5, characterized in that, The repair layer satisfies at least one of the following conditions: The pore size of the microchannel is 50nm-100nm; The spacing between the centers of two adjacent microchannels is 200nm-500nm; The cross-section of the microchannel perpendicular to the thickness of the repair layer is circular, elliptical, polygonal, or irregular.

7. The repair layer according to any one of claims 1-6, characterized in that, The polymer matrix is ​​doped with azobenzene; And / or, zinc oxide piezoelectric nanowires are embedded in the polymer matrix; Optionally, the mass content of azobenzene is 0.1%-2% based on the total mass of the polymer matrix; Optionally, the diameter of the zinc oxide piezoelectric nanowire is 10 nm-50 nm; Optionally, the mass content of zinc oxide piezoelectric nanowires is 1%-10% based on the total mass of the repair layer.

8. A perovskite solar cell, characterized in that, The perovskite solar cell includes a perovskite light-absorbing layer and a repair layer according to any one of claims 1-7, wherein the repair layer is located on at least a portion of the surface of the perovskite light-absorbing layer.

9. A stacked battery, characterized in that, The stacked cell includes the repair layer according to any one of claims 1-7, or the stacked cell includes the perovskite solar cell according to claim 8.

10. A photovoltaic module, characterized in that, The photovoltaic module includes the perovskite solar cell of claim 8, or the photovoltaic module includes the tandem cell of claim 9.

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