Anti-electrode corrosion trans-perovskite solar cell and preparation method thereof

Abstract

The present application relates to the technical field of perovskite battery, and discloses a trans perovskite solar cell resistant to electrode corrosion and a preparation method thereof, the cell comprising a conductive substrate, a hole transport layer, a perovskite layer, a surface passivation layer, a barrier layer, an electron transport layer and a silver electrode layer which are sequentially stacked from bottom to top; the material of the barrier layer comprises 2-mercaptobenzothiazole compounds and PCBM ((6,6)-phenyl-C61-butyric acid methyl ester); the 2-mercaptobenzothiazole compounds are one or more of 5-chloro-2-mercaptobenzothiazole, 5-bromo-2-mercaptobenzothiazole and 5-methyl-2-mercaptobenzothiazole. The present application inhibits the iodine-silver reaction from the source and the transmission process by setting the barrier layer, has strong protection pertinence, is not easy to introduce interface defects, and realizes the synergistic guarantee of the stability and photoelectric conversion efficiency of the cell.

Description

Technical Field

[0001] This invention relates to the technical field of perovskite solar cells, and in particular to an inverted perovskite solar cell resistant to electrode corrosion and its fabrication method. Background Technology

[0002] In the fabrication and application of inverted perovskite solar cells, silver electrodes have become the mainstream electrode material due to their excellent conductivity, low fabrication cost, and mature thin-film deposition technology, and are widely used in commercial research and development and pilot production. However, these cells are susceptible to distortion of the crystal structure of the perovskite active layer due to the coupling effects of multiple environmental factors such as light, operating temperature rise, and applied electric field, resulting in the continuous precipitation of iodine ions (I₂O₃). - The iodine species can be active iodine species such as iodine element (I₂). Driven by concentration gradients, these iodine species spontaneously diffuse and migrate to the silver electrode interface, undergoing irreversible chemical reactions with the silver electrode material. The main reaction equations are 2Ag + I₂ = 2AgI or Ag + I₂. - =AgI+e - During the iodine corrosion of the silver electrode, silver ions (Ag) generated by the corrosion reaction... + The silver iodide will migrate in the reverse direction into the perovskite active layer, further inducing a chain reaction at the interface, continuously promoting the formation of silver iodide corrosion products, forming a vicious cycle. This corrosion degradation process not only causes corrosion damage to the surface of the silver electrode and impairs the electrode's conductive pathway, leading to silver electrode failure and increased device series resistance, but also destroys the crystal integrity of the perovskite film, accelerates the decomposition and degradation of the perovskite active layer, and ultimately significantly reduces the photoelectric conversion efficiency of perovskite solar cells and shortens their actual working life, severely restricting the industrialization and long-term application of this type of battery.

[0003] To address the aforementioned technical challenges of silver electrode iodine corrosion and poor interface stability, the industry has developed various modification and optimization technologies to improve the interface compatibility and service stability of inverted perovskite solar cells. The mainstream technologies and their inherent limitations are detailed below: 1. Interface Barrier Layer Modification Technology: An inorganic dense barrier layer is introduced between the silver electrode and the charge transport layer. Commonly used materials include molybdenum trioxide (MoO3), titanium dioxide (TiO2), and lithium fluoride (LiF). Relying on the dense film structure of the barrier layer, the diffusion of active iodine species to the silver electrode side is physically blocked, while simultaneously inhibiting the reverse migration of silver ions generated during corrosion to the perovskite layer. Patent CN121908738A discloses a method for fabricating tandem solar cells, tandem solar cells, and photovoltaic modules. By evaporating inorganic rubidium salts, ion migration can be reduced by combining with surface-decomposed PbI2, thus improving device stability. However, the inorganic dense barrier layer is prone to uneven fabrication, introducing interface defects. These defects can form localized corrosion channels, significantly weakening the protective effect and requiring sophisticated deposition processes.

[0004] 2. Silver Electrode Modification Technology: There are two main modification methods: The first is silver-based alloying modification, which involves combining silver with metals such as copper and gold to prepare silver-based alloys such as Ag-Cu and Ag-Au. By altering the internal crystal structure of the silver material, the electrode's resistance to iodine corrosion is improved. The second is surface coating modification, which involves constructing protective coatings such as carbon layers or conductive polymers on the surface of the silver electrode. These coatings isolate iodine species from direct contact with the silver substrate, achieving corrosion protection. However, the conductivity of Ag alloys (such as Ag-Cu) is lower than that of pure Ag, which slightly reduces the electrode's current collection efficiency. If the surface coating (such as the carbon layer) is not tightly bonded, interface peeling is prone to occur, affecting long-term stability.

[0005] 3. Perovskite Layer Defect Passivation Technology: Intrinsic iodine vacancies are easily generated during the fabrication of perovskite films, and these defects are the main cause of iodine species escape and diffusion. The industry typically uses thiourea Lewis bases as passivating agents, utilizing the coordination effect between the passivating agent's functional groups and iodine vacancies to fill these defects in the perovskite layer, inhibiting the outward escape of internal active iodine species, reducing the reaction driving force of iodine corrosion from the source, and alleviating electrode corrosion problems. However, ordinary passivating agents mainly target surface defects in perovskite films, with a limited scope of action, and cannot eliminate iodine vacancies within the bulk phase of the film, thus having poor effectiveness in inhibiting the reaction between the silver electrode and the perovskite. Summary of the Invention

[0006] To address the aforementioned technical problems, this invention provides an electrode corrosion-resistant inverted perovskite solar cell and its preparation method. A 2-mercaptobenzothiazole compound and PCBM ((6,6)-phenyl-C61-butyrate methyl ester) are used as a barrier layer material, deposited between the perovskite layer and the silver electrode layer. This inhibits iodine ion migration and the reaction between the silver electrode and the perovskite, ensuring the perovskite solar cell has high photoelectric conversion efficiency.

[0007] The objective of this invention is achieved through the following technical solution: The present invention provides a trans - perovskite solar cell resistant to electrode corrosion. The cell includes a conductive substrate, a hole - transporting layer, a perovskite layer, a surface passivation layer, a blocking layer, an electron - transporting layer, and a silver electrode layer, which are stacked in sequence from bottom to top. The material of the perovskite layer is Cs x FA y MA 1-x-y Pb(I 1-z Br z )3, where 0 < x < 1, 0 < y < 1, 0 ≤ z < 1, FA is CH(NH2) 2+ , MA is CH3NH 3+ ; The material of the blocking layer includes 2 - mercaptobenzothiazole compounds and PCBM ((6,6) - phenyl - C61 - butyric acid methyl ester); The 2 - mercaptobenzothiazole compounds are one or more of 5 - chloro - 2 - mercaptobenzothiazole, 5 - bromo - 2 - mercaptobenzothiazole, and 5 - methyl - 2 - mercaptobenzothiazole.

[0008] The present invention uses 2 - mercaptobenzothiazole compounds and PCBM ((6,6) - phenyl - C61 - butyric acid methyl ester) as the blocking layer material, which is deposited on the surface of the perovskite layer. The 2 - mercaptobenzothiazole compounds can fill the residual iodine vacancies in the perovskite surface passivation layer through coordination, reducing the escape of iodine species from the source and decreasing the driving force of the corrosion reaction; The dense physical barrier of PCBM intercepts on the transmission path of iodine species and silver ions. Even if a small amount of iodine species escapes, it cannot penetrate the blocking layer and diffuse to the silver electrode interface, while blocking the reverse migration of silver ions to the perovskite layer, ultimately playing a role in inhibiting the reaction between the silver electrode and the perovskite.

[0009] Meanwhile, mixing 2 - mercaptobenzothiazole compounds with PCBM can effectively improve the dispersion of PCBM in solution and optimize the film uniformity. The fullerene cage in PCBM is a strong conjugated structure, and molecules are prone to form nanocrystalline clusters through π - π stacking. Due to its special molecular structure characteristics, it is easy to aggregate during spin - coating to form a film, reducing the uniformity / coverage. The benzothiazole aromatic ring of 2 - mercaptobenzothiazole compounds is a rigid hydrophobic group, which can form steric hindrance, preventing the close contact between PCBM molecules, breaking the driving force of π - π stacking, and optimizing the dispersion of PCBM in solution.

[0010] Introducing substituents onto the benzene ring of 2-mercaptobenzothiazole molecule can further enhance its effect on improving the uniformity of PCBM film formation, surpassing that of unsubstituted 2-mercaptobenzothiazole. This optimizes the synergistic blocking effect between 2-mercaptobenzothiazole compounds and PCBM. Substituents can regulate the electron distribution, molecular dipole moment, and steric hindrance of 2-mercaptobenzothiazole, strengthening the specific interaction between its thiol group (-SH) and thiazole ring and PCBM, weakening the π-π stacking and C=O dipole aggregation between PCBM molecules, and inhibiting PCBM molecule aggregation, thereby significantly improving the compactness and morphological uniformity of the PCBM film. The substituent site on the benzene ring has a significant impact on the improvement of PCBM film uniformity, with the 5-position (para-position) being the optimal substitution position, showing a better effect on improving film uniformity than the 4 / 6-position (ortho-position) and the 7-position (meta-position). Substituents at the 5-position enable efficient transfer of electronic effects through the conjugated system without disrupting molecular planarity or interfacial adsorption orientation. This facilitates stable and oriented interfacial interactions, allowing for precise control over the crystallization and morphology of PCBM. In contrast, 4 / 6-position substitutions are prone to steric hindrance, while 7-position substitutions suffer from low electronic effect transfer efficiency and improper dipole orientation, both of which significantly weaken the improvement on PCBM film uniformity.

[0011] Preferably, the mass ratio of the 2-mercaptobenzothiazole compound to PCBM is 1:10~30.

[0012] The structural formulas of the 2-mercaptobenzothiazole compounds are as follows: R1 is chlorine, bromine or methyl.

[0013] Preferably, the thickness of the perovskite layer is 500~700nm; and the thickness of the barrier layer is 5~30nm.

[0014] Preferably, the material of the surface passivation layer includes phenylethyl ammonium chloride or phenylethyl ammonium iodide; the thickness of the surface passivation layer is 5~30 nm.

[0015] Preferably, the hole transport layer is made of [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid (2PACz), [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz), or [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid (Me-4PACz); the thickness of the hole transport layer is 5~20 nm.

[0016] Preferably, the electron transport layer comprises a C60 layer and a SnO2 layer stacked sequentially from bottom to top; the thickness of the electron transport layer is 30~60nm.

[0017] Preferably, the thickness of the silver electrode layer is 100~200 nm.

[0018] Preferably, the conductive substrate comprises FTO glass or ITO glass.

[0019] Secondly, the present invention also provides a method for preparing an inverted perovskite solar cell resistant to electrode corrosion, comprising the following steps: sequentially depositing a hole transport layer, a perovskite layer, a surface passivation layer and a barrier layer on a conductive substrate by spin coating followed by annealing; and sequentially depositing an electron transport layer and a silver electrode layer on the barrier layer by vapor deposition to obtain an inverted perovskite solar cell.

[0020] Preferably, after spin-coating the barrier layer solution onto the surface passivation layer, the barrier layer is annealed to obtain the barrier layer; the barrier layer solution is an isopropanol solution of 2-mercaptobenzothiazole compound and PCBM, wherein the concentration of 2-mercaptobenzothiazole compound is 0.1~10 mg / mL and the concentration of PCBM is 0.1~10 mg / mL.

[0021] Preferably, the annealing temperature is 90~110℃ and the time is 5~20min.

[0022] Compared with the prior art, the present invention has the following beneficial effects: (1) This invention inhibits the silver iodine reaction from both the source and the transport process by setting a barrier layer (2-mercaptobenzothiazole compound + PCBM), which provides strong protection. At the same time, the mixing of 2-mercaptobenzothiazole compound and PCBM can effectively improve the dispersibility of PCBM in solution and optimize the film uniformity, which can further optimize the synergistic barrier effect of 2-mercaptobenzothiazole compound and PCBM. (2) This invention does not involve the modification of the silver electrode, and can completely retain the excellent conductivity of the silver electrode itself; at the same time, the barrier layer material used has stable chemical properties and good energy level matching with the subsequently deposited electron transport layer and hole transport layer, and will not cause problems such as a decrease in carrier mobility or an increase in charge recombination, thus achieving synergistic protection of battery stability and photoelectric conversion efficiency. (3) The barrier layer can be prepared by conventional solution deposition, which is simple to operate and has a higher tolerance for film thickness uniformity. Furthermore, the mixed solvent system has good compatibility with the perovskite surface passivation layer, and is not prone to introducing interface defects, which is conducive to promoting industrial production. Attached Figure Description

[0023] Figure 1 This is a schematic diagram of the structure of the inverted perovskite solar cell in this invention.

[0024] The attached figures are labeled as follows: 1. Conductive substrate; 2. Hole transport layer; 3. Perovskite layer; 4. Surface passivation layer; 5. Barrier layer; 6. Electron transport layer; 7. Silver electrode layer.

[0025] Figure 2 This is a comparison image of unencapsulated perovskite solar cells from Example 2 and Comparative Example 1 after accelerated aging at 120°C and 1 sun illumination for 14 days.

[0026] Figure 3 The ToF-SIMS distribution of iodine in the unencapsulated perovskite solar cell of Comparative Example 1 after accelerated aging at 120 degrees and 1 sun illumination for 14 days is shown in the longitudinal direction (Z-axis, depth dimension). (Left: before aging; Right: after aging)

[0027] Figure 4 The image shows the ToF-SIMS distribution of iodine in the unencapsulated perovskite solar cell after accelerated aging at 120 degrees and 1 sun illumination for 14 days in Example 2 (left: before aging; right: after aging). Detailed Implementation

[0028] The technical solution of the present invention will be illustrated below with specific embodiments, but the scope of protection of the present invention is not limited thereto.

[0029] like Figure 1 As shown, the electrode corrosion resistant inverted perovskite solar cell of the present invention includes a conductive substrate 1, a hole transport layer 2, a perovskite layer 3, a surface passivation layer 4, a barrier layer 5, an electron transport layer 6, and a silver electrode layer 7, which are stacked sequentially from bottom to top.

[0030] The fabrication of the above-mentioned inverted perovskite solar cells includes the following steps: S1. Transparent conductive substrate treatment: FTO glass is ultrasonically cleaned with cleaning agent, deionized water, acetone and isopropanol respectively, then dried with nitrogen and treated in a UV ozone cleaner to obtain the treated transparent conductive substrate. S2. Hole transport layer preparation: Prepare a Me-4PACz ([4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid) solution with ethanol, spread the Me-4PACz solution on the treated transparent conductive substrate, and spin-coat it; after spin-coating, anneal at 90~110℃ for 5~20 min to obtain a hole transport layer with a thickness of 5~20 nm; S3. Perovskite Layer Preparation: The material of the perovskite layer is Cs. x FA y MA 1-x-y Pb(I 1-z Br z)3, where 0 < x < 1, 0 < y < 1, 0 ≤ z < 1, and FA is CH(NH2) 2+ , and MA is CH3NH 3+ ; In a mixed solvent of DMF and DMSO, prepare a perovskite precursor solution according to the chemical formula, spread the perovskite solution on the hole transport layer, first spin-coat at a low speed of 1000 - 2000 rpm for 10 - 20 s, then spin-coat at a high speed of 4000 - 5000 rpm for 20 - 40 s, and dropwise add chlorobenzene solvent at the 5th second from the end of the high-speed stage; After the spin-coating is completed, the sample is first annealed at 90 - 110 °C for 50 - 70 min, and then annealed at 150 - 160 °C for 10 - 20 min to obtain a perovskite layer with a thickness of 500 - 700 nm; S4. Preparation of the surface passivation layer: Prepare a PEACl (phenethylammonium chloride) solution with isopropyl alcohol, spread the PEACl solution on the perovskite layer, and perform spin-coating; After the spin-coating is completed, anneal at 90 - 110 °C for 5 - 20 min to obtain a surface passivation layer with a thickness of 5 - 30 nm; S5. Preparation of the blocking layer: Mix a 2-mercaptobenzothiazole compound (one or more of 5-chloro-2-mercaptobenzothiazole, 5-bromo-2-mercaptobenzothiazole, and 5-methyl-2-mercaptobenzothiazole) with PCBM and dissolve it in isopropyl alcohol to prepare a blocking layer solution with a concentration of 0.1 - 10 mg / mL for the 2-mercaptobenzothiazole compound and a concentration of 0.1 - 10 mg / mL for PCBM; Spread the blocking layer solution on the surface passivation layer and spin-coat at a speed of 4000 - 5000 rpm for 20 - 40 s; After the spin-coating is completed, anneal at 90 - 110 °C for 5 - 20 min to obtain a blocking layer with a thickness of 5 - 30 nm; S6. Preparation of the electron transport layer: Deposit C60 on the blocking layer by vacuum thermal evaporation with a thickness of 20 - 30 nm; and transfer it to an atomic layer deposition system (ALD) to deposit SnO2 with a thickness of 10 - 30 nm; The total thickness of the electron transport layer is 30 - 60 nm; S7. Preparation of the silver electrode layer: Evaporate a layer of silver on the electron transport layer by vacuum thermal evaporation with a thickness of 100 - 200 nm; A reverse perovskite solar cell is fabricated.[[ID=!13]]

[0031] Example 1

[0032] In this example, the reverse perovskite solar cell includes a conductive substrate, a hole transport layer, a perovskite layer, a surface passivation layer, a blocking layer, an electron transport layer, and a silver electrode layer stacked in sequence from bottom to top.

[0033] The preparation of the above reverse perovskite solar cell includes the following steps: S1. Transparent conductive substrate treatment: FTO glass is ultrasonically cleaned for 15 minutes with cleaning agent, deionized water, acetone and isopropanol respectively, then dried with nitrogen and treated in ultraviolet ozone cleaner for 20 minutes to obtain the treated transparent conductive substrate. S2. Hole transport layer preparation: A Me-4PACz ([4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid) solution was prepared with ethanol. The Me-4PACz solution was spread on the treated transparent conductive substrate and spin-coated at 4000 rpm for 30 s. After spin-coating, the substrate was annealed at 100℃ for 10 min to obtain a hole transport layer with a thickness of 10 nm. S3. Perovskite Layer Preparation: The material of the perovskite layer is Cs. 0.05 FA 0.8 MA 0.15 Pb(I 0.75 Br 0.25 )3, where FA is CH(NH2) 2+ MA is CH3NH 3+ A 1.4 mol / L perovskite precursor solution was prepared in a mixed solvent of DMF:DMSO at a volume ratio of 4:1 according to the chemical formula. 85 μL of the perovskite solution was spread on the hole transport layer. The solution was first spin-coated at a low speed of 2000 rpm for 10 s, and then at a high speed of 4000 rpm for 30 s. 150 μL of chlorobenzene solvent was added dropwise in the 5th second before the end of the high-speed stage. After spin-coating, the sample was annealed at 100℃ for 60 min and then at 150℃ for 10 min to obtain a perovskite layer with a thickness of 600 nm. S4. Preparation of surface passivation layer: PEACl (phenylethyl ammonium chloride) solution was prepared with isopropanol, and the PEACl solution was spread on the perovskite layer and spin-coated at 4500 rpm for 25s; after spin-coating, it was annealed at 90℃ for 10min to obtain a surface passivation layer with a thickness of 10nm. S5. Barrier layer preparation: 2-Mercaptobenzothiazole compound (5-bromo-2-mercaptobenzothiazole) was mixed with PCBM and dissolved in isopropanol to prepare a barrier layer solution with a concentration of 0.4 mg / mL of 2-mercaptobenzothiazole compound and a concentration of 4 mg / mL of PCBM; 100 μL of the barrier layer solution was spread on the surface passivation layer and spin-coated at 5000 rpm for 25 s; after spin-coating, it was annealed at 90℃ for 10 min to obtain a barrier layer with a thickness of 10 nm; S6. Electron transport layer preparation: C60 with a thickness of 20 nm was deposited on the barrier layer by vacuum thermal evaporation; and then transferred to an atomic layer deposition system (ALD) to deposit SnO2 with a thickness of 15 nm; the total thickness of the electron transport layer is 35 nm. S7. Silver electrode layer preparation: A layer of silver with a thickness of 120 nm is deposited on the electron transport layer by vacuum thermal evaporation; thus, an inverted perovskite solar cell is obtained.

[0034] Example 2

[0035] The only difference between this embodiment and Example 1 is that 5-bromo-2-mercaptobenzothiazole is replaced with 5-chloro-2-mercaptobenzothiazole.

[0036] Example 3

[0037] The only difference between this embodiment and Example 1 is that 5-bromo-2-mercaptobenzothiazole is replaced with 5-methyl-2-mercaptobenzothiazole.

[0038] Example 4

[0039] The only difference between this embodiment and Embodiment 1 is that the material of the perovskite layer is Cs. 0.05 FA 0.95 PbI3, where FA is CH(NH2). 2+ .

[0040] Example 5

[0041] The only difference between this embodiment and Example 1 is that the concentration of 2-mercaptobenzothiazole compounds in the barrier layer solution is 0.2 mg / mL and the concentration of PCBM is 4.0 mg / mL.

[0042] Comparative Example 1 The only difference between this comparative example and Example 1 is that a barrier layer is not used. In this comparative example, the inverted perovskite solar cell includes, from bottom to top, a conductive substrate, a hole transport layer, a perovskite layer, a surface passivation layer, an electron transport layer, and a silver electrode layer.

[0043] Comparative Example 2 The only difference between this comparative example and Example 1 is that 5-bromo-2-mercaptobenzothiazole is replaced with 2-mercaptobenzothiazole.

[0044] Comparative Example 3 The only difference between this comparative example and Example 1 is that 5-bromo-2-mercaptobenzothiazole is replaced with 4-bromo-2-mercaptobenzothiazole.

[0045] Comparative Example 4 The only difference between this comparative example and Example 1 is that 5-bromo-2-mercaptobenzothiazole is replaced with 6-bromo-2-mercaptobenzothiazole.

[0046] Comparative Example 5 The only difference between this comparative example and Example 1 is that 5-bromo-2-mercaptobenzothiazole is replaced with 7-bromo-2-mercaptobenzothiazole.

[0047] Comparative Example 6 The only difference between this comparative example and Example 1 is that the barrier layer includes a 5-bromo-2-mercaptobenzothiazole layer and a PCBM layer stacked sequentially from bottom to top.

[0048] The fabrication of inverted perovskite solar cells includes the following steps: Steps S1-S4 are the same as in Example 1; S5. Barrier Layer Preparation: 2-Mercaptobenzothiazole compound (5-bromo-2-mercaptobenzothiazole) and PCBM were dissolved in isopropanol to prepare a 0.4 mg / mL 2-mercaptobenzothiazole compound solution and a 4 mg / mL PCBM solution. 100 μL of the 2-mercaptobenzothiazole compound solution was spread on the surface passivation layer and spin-coated at 5000 rpm for 25 s. After spin-coating, the solution was annealed at 90 °C for 10 min to obtain a 5-bromo-2-mercaptobenzothiazole layer. 50 μL of PCBM solution was spread on the 5-bromo-2-mercaptobenzothiazole layer and spin-coated at 5000 rpm for 25 s. After spin-coating, the solution was annealed at 90 °C for 10 min to obtain a PCBM layer. The total thickness of the barrier layer was 10 nm. Steps S6-S7 are the same as in Example 1, and an inverted perovskite solar cell is obtained.

[0049] Comparative Example 7 The only difference between this comparative example and Example 1 is that the concentration of 2-mercaptobenzothiazole compounds in the barrier layer solution is 1.0 mg / mL and the concentration of PCBM is 4.0 mg / mL.

[0050] The inverse perovskite solar cells in Examples 1-5 and Comparative Examples 1-7 were subjected to performance tests under standard test conditions (illuminance: 1000 W / m²). 2 Temperature: 25℃; Spectrum: AM 1.5G. The test results are shown in Table 1.

[0051] Table 1 Battery performance test results

[0052] like Figure 2 The image shows a comparison of unencapsulated perovskite solar cells after accelerated aging at 120 degrees Celsius and 1 sun illumination for 14 days. As can be seen from the image, in Comparative Example 1, the silver electrode has turned black over a large area, indicating black AgI corrosion caused by iodine. In Example 2, only part of the silver electrode has turned black, but the preservation condition is relatively good.

[0053] like Figure 3The figure shows the ToF-SIMS distribution of iodine in the perovskite solar cell in Comparative Example 1 along the longitudinal direction (Z-axis, depth dimension) (color depth corresponds to signal intensity). The left figure shows the ToF-SIMS distribution of iodine in the longitudinal direction of the cell before aging (initial state): the overall signal intensity is uniform, with no significant local enrichment or diffusion characteristics, reflecting that the distribution of iodine in the perovskite film is stable in the initial state. The right figure shows the ToF-SIMS distribution of iodine after the cell has been accelerated to age at 120℃ and 1 sun for 14 days: after aging, there is a significant enhancement of the iodine signal in the sample surface area (Z≈0~10 frames) (color shifts to the higher value range), indicating that without a barrier layer, iodine in the perovskite underwent significant longitudinal migration (aggregation to the surface) during the aging process. The strong migration behavior of iodine ions led to the corrosion of the silver electrode.

[0054] like Figure 4 The image shows the ToF-SIMS distribution of iodine in the perovskite solar cell in Example 2 along the longitudinal direction (Z-axis, depth dimension) (color depth corresponds to signal intensity). The left image shows the ToF-SIMS distribution of iodine in the longitudinal direction of the cell before aging (initial state): In the initial state, the iodine signal distribution characteristics are similar to... Figure 3 center left Figure 1 This indicates that the introduction of the barrier layer did not interfere with the initial iodine distribution in the perovskite. The right figure shows the ToF-SIMS distribution of iodine in the battery after accelerated aging at 120℃ and 1 sun for 14 days: the iodine signal in the sample surface area did not show a significant enhancement after aging, and the overall distribution characteristics were not significantly different from the initial state (left figure), indicating that the barrier layer effectively suppressed the migration behavior of iodine during the aging process, and the perovskite battery has good stability.

[0055] As shown in Table 1, Examples 1-3 exhibit higher photoelectric conversion efficiencies compared to Comparative Example 1, indicating that the barrier layer in this invention effectively suppresses iodine migration. Furthermore, a comparison between Comparative Examples 2-5 and Example 1 shows that whether or not substituents are introduced onto the benzene ring of 2-mercaptobenzothiazole and the substitution positions of these substituents affect the synergistic effect between the 2-mercaptobenzothiazole compounds and the PCBM, thus reducing the iodine barrier effect and consequently lowering the photoelectric conversion efficiency of the perovskite solar cell. A comparison between Comparative Example 6 and Example 1 shows that the 2-mercaptobenzothiazole compounds and PCBM in the barrier layer were not mixed but prepared separately in layers. This resulted in poorer film uniformity of the PCBM layer, leading to a weaker barrier effect. Moreover, the 2-mercaptobenzothiazole compound layer also exhibited a weaker barrier effect due to the lack of physical barrier properties provided by the PCBM, further reducing the photoelectric conversion efficiency of the perovskite solar cell. Comparison of Example 7 with Examples 1 and 5 shows that the relative ratio of 2-mercaptobenzothiazole compounds to PCBM in the barrier layer also affects the barrier effect on iodine. An excessively high proportion of 2-mercaptobenzothiazole compounds can have a negative effect on the film formation of PCBM and affect the potential of the barrier layer and its energy level matching with the layers of the battery, thus reducing the battery efficiency.

[0056] The above are merely preferred embodiments of the present invention and do not limit the patent scope of the present invention. Any equivalent structural or procedural transformations made using the present invention specification, or direct or indirect applications in other related technical fields, are similarly included within the patent protection scope of the present invention.

Claims

1. A trans-perovskite solar cell resistant to electrode corrosion, characterized in that, The battery includes a conductive substrate, a hole transport layer, a perovskite layer, a surface passivation layer, a blocking layer, an electron transport layer, and a silver electrode layer that are stacked in sequence from bottom to top; the material of the perovskite layer is Cs x FA y MA 1-x-y Pb(I 1-z Br z )3, where 0 < x < 1, 0 < y < 1, 0 ≤ z < 1; the material of the blocking layer includes 2-mercaptobenzothiazole compounds and PCBM; the 2-mercaptobenzothiazole compounds are one or more of 5-chloro-2-mercaptobenzothiazole, 5-bromo-2-mercaptobenzothiazole, and 5-methyl-2-mercaptobenzothiazole.

2. The electrode corrosion-resistant inverse perovskite solar cell according to claim 1, characterized in that, The mass ratio of the 2-mercaptobenzothiazole compound to PCBM is 1:10~30.

3. The electrode corrosion-resistant inverse perovskite solar cell according to claim 1 or 2, characterized in that, The thickness of the perovskite layer is 500~700nm; the thickness of the barrier layer is 5~30nm.

4. The electrode corrosion-resistant inverse perovskite solar cell according to claim 1, characterized in that, The material of the surface passivation layer includes phenylethyl ammonium chloride or phenylethyl ammonium iodide; the thickness of the surface passivation layer is 5~20 nm.

5. The electrode corrosion-resistant inverse perovskite solar cell according to claim 1, characterized in that, The thickness of the silver electrode layer is 100~200 nm.

6. The electrode corrosion-resistant inverse perovskite solar cell according to claim 1, 4, or 5, characterized in that, The electron transport layer comprises a C60 layer and a SnO2 layer stacked sequentially from bottom to top; the thickness of the electron transport layer is 30~60nm.

7. The electrode corrosion-resistant inverse perovskite solar cell according to claim 1, 4, or 5, characterized in that, The hole transport layer is made of [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid, [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid, or [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid; the thickness of the hole transport layer is 5~20 nm.

8. A method for preparing an inverse perovskite solar cell resistant to electrode corrosion as described in any one of claims 1-7, characterized in that, The process includes the following steps: depositing a hole transport layer, a perovskite layer, a surface passivation layer, and a barrier layer sequentially on a conductive substrate by spin coating followed by annealing; and depositing an electron transport layer and a silver electrode layer sequentially on the barrier layer by vapor deposition to obtain an inverted perovskite solar cell.

9. The method for preparing the electrode corrosion-resistant inverse perovskite solar cell according to claim 8, characterized in that, After spin-coating a barrier layer solution onto the surface passivation layer, the barrier layer is annealed to obtain the barrier layer; the barrier layer solution is an isopropanol solution of 2-mercaptobenzothiazole compound and PCBM, wherein the concentration of 2-mercaptobenzothiazole compound is 0.1~10 mg / mL and the concentration of PCBM is 0.1~10 mg / mL.

10. The method for preparing an electrode corrosion-resistant inverse perovskite solar cell according to claim 8 or 9, characterized in that, The annealing temperature is 90~110℃ and the time is 5~20min.

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