Perovskite solar cell, preparation method thereof and photovoltaic module
By introducing dibenzophenone ultraviolet absorbers into perovskite solar cells, the problem of easy degradation of perovskite solar cells under ultraviolet light is solved, and their stability and service life are improved.
Patent Information
- Application Number
- CN202410250562.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-03-05
- Publication Date
- 2025-09-05
AI Technical Summary
Perovskite solar cells are susceptible to degradation under ultraviolet light, resulting in poor stability.
Benzophenone ultraviolet absorbers are introduced into the stacked structure of perovskite solar cells as a functional layer or mixed with perovskite active materials to absorb ultraviolet light and inhibit ion migration and charge transport in perovskite films.
The stability and service life of perovskite solar cells are improved, and the degradation of perovskite active materials by ultraviolet light is inhibited.
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Figure CN120603428A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of perovskite solar cell preparation, and in particular to a perovskite solar cell, a preparation method thereof, and a photovoltaic module. Background Art
[0002] For PSCs, achieving long-term stability of perovskite solar cells in natural environments and under ultraviolet (UV) irradiation remains a huge challenge. This instability of perovskites mainly stems from the defect chemistry of perovskites. Many inevitable defects are formed on the surface and grain boundaries of polycrystalline perovskite films, which further accelerate the degradation process of perovskites and ultimately lead to PCE degradation. Under sunlight irradiation including UVa (320-400nm) and UVb (280-320nm), the decomposition of perovskite active materials is almost impossible to suppress. In particular, strong UVb light can easily destroy lead-containing perovskite devices, thereby inducing Pb 2+ The valence of Pb is changed to Pb, which leads to the emergence of deep energy level defect states in the perovskite film, seriously degrading the performance of PSCs and their stability.
[0003] Potential UV-absorbing passivation materials primarily include benzophenone and its derivatives, or other UV-absorbing organic compounds. These organic compounds contain functional groups that can passivate grain boundary defects. However, there are few reports on the application of benzophenone-based UV absorbers in perovskite solar cells, and the passivation effect needs to be improved.
[0004] Therefore, researching and developing a benzophenone-based UV absorber for perovskite solar cells is of great significance for improving the stability of perovskite solar cells. Summary of the Invention
[0005] The main purpose of the present invention is to provide a perovskite solar cell, a preparation method thereof and a photovoltaic module to solve the problem of poor stability caused by poor resistance to ultraviolet degradation of perovskite solar cells in the prior art.
[0006] To achieve the above objectives, the present invention provides a perovskite solar cell, comprising a stacked transparent conductive substrate, a hole transport layer, a perovskite active layer, an electron transport layer, an interface layer, and a metal electrode layer; the perovskite solar cell further comprises a functional layer, the functional layer being disposed between the transparent conductive substrate and the hole transport layer, or between the hole transport layer and the perovskite active layer, wherein the material of the functional layer is a benzophenone ultraviolet absorber; and / or the material of the perovskite active layer is a perovskite active material, or a mixture of a benzophenone ultraviolet absorber and a perovskite active material;
[0007] Among them, the benzophenone ultraviolet absorber has a structure shown in the general formula (I):
[0008]
[0009] R1 and R1' are independently selected from hydrogen or -OH; R2 and R2' are independently selected from hydrogen, -COOH, -OH or C1-C5 alkoxy; R3 and R3' are independently selected from hydrogen, -OH, C1-C5 alkoxy, C1-C5 alkyl, halogen, C1-C5 haloalkyl, cyano, amino, 1 or 2 C2-C5 alkyl-substituted amines, C2-C5 alkyl-substituted amides, or a C1-C5 alkyl-substituted mercapto group; R4 and R4' are independently selected from hydrogen or -OH; R5 and R5' are independently selected from hydrogen, -OH or halogen; or, R5 and R5' are linked to form -C(=O)- or -S-.
[0010] Furthermore, R2 and R2' are both hydrogen, or one of them is -COOH and the other is hydrogen, or one of them is -OH and the other is hydrogen, or one of them is methoxy and the other is hydrogen; R3 and R3' are independently selected from hydrogen, -OH, methoxy, methyl, fluorine, chlorine, cyano, amino, -CF3, or methylthio; R4 and R4', one of which is -OH and the other is hydrogen, or both are hydrogen; R5 and R5' are independently selected from hydrogen, -OH, bromine or chlorine.
[0011] Furthermore, the benzophenone ultraviolet absorber is selected from any one or more of the following structures:
[0012]
[0013]
[0014]
[0015]
[0016] Furthermore, when the material of the perovskite active layer is a mixture of a benzophenone ultraviolet absorber and a perovskite active material, the weight percentage of the benzophenone ultraviolet absorber is 0.5 to 5.0 wt % based on the total weight of the perovskite active layer.
[0017] Furthermore, the thickness of the functional layer is 10-100 nm.
[0018] To achieve the above objectives, another aspect of the present invention further provides a method for preparing the above-mentioned perovskite solar cell provided in the present application, wherein a hole transport layer, a perovskite active layer, an electron transport layer, an interface layer and a metal electrode layer are sequentially prepared on the conductive surface side of a transparent conductive substrate; the preparation method also includes preparing a functional layer on the conductive surface side of the transparent conductive substrate, or on the surface of the hole transport layer close to the perovskite active layer, and the preparation process of the functional layer includes: mixing a dibenzophenone ultraviolet absorber with a first solvent to obtain a first mixed liquid, coating the first mixed liquid on the conductive surface side of the transparent conductive substrate, or on the surface of the hole transport layer close to the perovskite active layer, and obtaining the functional layer after heat treatment.
[0019] Furthermore, the preparation process of the perovskite active layer includes: mixing a perovskite active material precursor, or a mixture of a dibenzophenone ultraviolet absorber and a perovskite active material precursor with a second solvent to obtain a second mixed liquid, coating the second mixed liquid on the surface of the hole transport layer away from the transparent conductive substrate, and obtaining the perovskite active layer after annealing.
[0020] Furthermore, during the preparation of the functional layer, the heat treatment temperature is 100-150° C. and the time is 10-15 minutes.
[0021] Furthermore, the first mixed liquid is coated by spin coating, preferably with a spin coating speed of 2000 to 5000 rpm and a spin coating time of 20 to 50 s.
[0022] Furthermore, the first solvent is selected from one or more of the group consisting of DMF, DMSO and γ-butyrolactone.
[0023] Furthermore, during the preparation of the perovskite active layer, the annealing temperature is 100-150° C. and the time is 10-15 minutes.
[0024] Furthermore, the second mixed liquid is coated by spin coating, preferably firstly at a rotation speed of 1000-2000 rpm for 10-40 seconds, and then at a rotation speed of 4000-6000 rpm for 10-20 seconds.
[0025] Furthermore, the second solvent is selected from one or more of the group consisting of DMF, DMSO and γ-butyrolactone, and is preferably a mixed solvent of DMF and DMSO.
[0026] Furthermore, the perovskite active material precursor is selected from one or more of the group consisting of FAPbI3, MAPbI3, FAPbBr3, MAPbBr3, CsBr and CsI.
[0027] A photovoltaic module, comprising the perovskite solar cell provided in this application.
[0028] By applying the technical solution of the present invention, compared with traditional benzophenone derivatives, the above-mentioned specific types of benzophenone ultraviolet absorbers have specific functional groups, such as hydroxyl, amino, amide, halogen, etc. These specific functional groups can enhance the interaction between molecules, so that these benzophenone ultraviolet absorbers can be better accumulated, thereby improving the absorption effect of ultraviolet rays, which is beneficial to inhibiting ion migration in perovskite films and improving charge transfer at perovskite grain boundaries, thereby improving the stability of perovskite solar cells and extending their service life. BRIEF DESCRIPTION OF THE DRAWINGS
[0029] The accompanying drawings, which constitute part of this application, are intended to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are intended to explain the present invention and do not constitute an undue limitation of the present invention. In the accompanying drawings:
[0030] Figure 1 A schematic diagram of the stacked structure of a traditional perovskite solar cell is shown;
[0031] Figure 2 A schematic diagram of the stacked structure of a perovskite solar cell according to a preferred embodiment of the present invention is shown;
[0032] Figure 3 A schematic diagram of the stacked structure of a perovskite solar cell according to another preferred embodiment of the present invention is shown.
[0033] The above drawings include the following reference numerals:
[0034] 10. Transparent conductive substrate; 20. Hole transport layer; 30. Perovskite active layer; 40. Electron transport layer; 50. Interface layer; 60. Metal electrode layer; 70. Functional layer. DETAILED DESCRIPTION
[0035] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below with reference to the embodiments.
[0036] As described in the background art, existing perovskite solar cells have poor resistance to ultraviolet degradation, resulting in poor stability. In order to solve the above technical problems, the first aspect of the present application provides a perovskite solar cell, such as Figure 1 As shown, the perovskite solar cell includes a transparent conductive substrate 10, a hole transport layer 20, a perovskite active layer 30, an electron transport layer 40, an interface layer 50 and a metal electrode layer 60, which are stacked. The perovskite solar cell also includes a functional layer 70, which is arranged between the transparent conductive substrate 10 and the hole transport layer 20 (as shown in FIG. Figure 2), or between the hole transport layer 20 and the perovskite active layer 30 (as shown Figure 3 As shown), the material of the functional layer 70 is a benzophenone ultraviolet absorber; and / or the material of the perovskite active layer 30 is a perovskite active material, or a mixture of a benzophenone ultraviolet absorber and a perovskite active material; wherein the benzophenone ultraviolet absorber has a structure shown in general formula (I):
[0037]
[0038] R1 and R1' are independently selected from hydrogen or -OH; R2 and R2' are independently selected from hydrogen, -COOH, -OH or C1-C5 alkoxy; R3 and R3' are independently selected from hydrogen, -OH, C1-C5 alkoxy, C1-C5 alkyl, halogen, C1-C5 haloalkyl, cyano, amino, 1 or 2 C2-C5 alkyl-substituted amines, C2-C5 alkyl-substituted amides, or a C1-C5 alkyl-substituted mercapto group; R4 and R4' are independently selected from hydrogen or -OH; R5 and R5' are independently selected from hydrogen, -OH or halogen; or, R5 and R5' are linked to form -C(=O)- or -S-.
[0039] In the perovskite solar cell provided in the present application, between the transparent conductive substrate 10 and the hole transport layer 20 (eg Figure 2 ), or between the hole transport layer 20 and the perovskite active layer 30 (as shown Figure 3 As shown in the figure, a functional layer 70 with a specific composition is provided. When sunlight irradiates the cell, the benzophenone ultraviolet absorber of the functional layer 70 can absorb ultraviolet light, so that the ultraviolet light is absorbed before it enters the perovskite active layer 30, thereby inhibiting the degradation of the perovskite active material by ultraviolet light and improving the stability of the perovskite solar cell. When the above-mentioned benzophenone ultraviolet absorber is used together with the perovskite active material as the material of the perovskite active layer 30, the benzophenone ultraviolet absorber can passivate the perovskite lattice and surface defects, inhibiting the Pb in the perovskite active material. 2+ It is converted into Pb, which can inhibit ultraviolet degradation, inhibit ion migration in perovskite films, and improve charge transfer at perovskite grain boundaries, thereby significantly improving the stability of perovskite solar cells.
[0040] Compared with traditional benzophenone derivatives, the above-mentioned specific types of benzophenone UV absorbers have specific functional groups, such as hydroxyl, amino, amide, halogen, etc. These specific functional groups can enhance the interaction between molecules, so that these benzophenone UV absorbers can be better accumulated, thereby improving the absorption effect of ultraviolet rays, which is beneficial to inhibiting ion migration in perovskite films and improving charge transfer at perovskite grain boundaries, thereby improving the stability of perovskite solar cells and extending their service life.
[0041] In a preferred embodiment, R2 and R2' are both hydrogen, or one of them is -COOH and the other is hydrogen, or one of them is -OH and the other is hydrogen, or one of them is methoxy and the other is hydrogen; R3 and R3' are independently selected from but not limited to hydrogen, -OH, methoxy, methyl, fluorine, chlorine, cyano, amino, -CF3, or methylthio; one of R4 and R4' is -OH and the other is hydrogen, or both are hydrogen; R5 and R5' independently include, but are not limited to, hydrogen, -OH, bromine, or chlorine. Compared to other types, the use of the above-mentioned R2, R2', R3, R3', R4, R4', R5, and R5' is beneficial for increasing the absorbance of benzophenone-based UV absorbers to ultraviolet light (especially ultraviolet light in the range of 250nm to 350nm), thereby improving the stability of perovskite solar cells.
[0042] In a preferred embodiment, the benzophenone ultraviolet absorber includes but is not limited to any one or more of the following structures:
[0043]
[0044]
[0045]
[0046] Compared with other types, the dibenzophenone ultraviolet absorber with the above structure has a higher absorbance to ultraviolet light, especially ultraviolet light in the range of 250nm to 350nm, which is beneficial to further improve the stability of perovskite solar cells.
[0047] In a preferred embodiment, when the material of the perovskite active layer 30 is a mixture of a benzophenone-based UV absorber and a perovskite active material, the weight percentage of the benzophenone-based UV absorber is 0.5-5.0 wt % based on the total weight of the perovskite active layer 30. The weight percentage of the benzophenone-based UV absorber includes, but is not limited to, the aforementioned range. Limiting the benzophenone-based UV absorber to the aforementioned range is beneficial for enhancing the benzophenone-based UV absorber's ability to absorb UV rays, thereby suppressing the degradation of the perovskite active material by UV light, and thereby improving the stability of the perovskite solar cell.
[0048] In a preferred embodiment, the thickness of the functional layer 70 is 10 to 100 nm. The thickness of the functional layer 70 includes, but is not limited to, the aforementioned range. Limiting the thickness of the functional layer 70 to the aforementioned range is beneficial for maintaining excellent conductivity of the perovskite solar cell while allowing the functional layer 70 to absorb ultraviolet rays, thereby minimizing the impact of the introduction of the functional layer 70 on the electrochemical performance of the cell.
[0049] The second aspect of the present application also provides a method for preparing a perovskite solar cell, wherein a hole transport layer 20, a perovskite active layer 30, an electron transport layer 40, an interface layer 50 and a metal electrode layer 60 are sequentially prepared on the conductive surface side of a transparent conductive substrate 10; the above-mentioned preparation method also includes preparing a functional layer 70 on the conductive surface side of the transparent conductive substrate 10, or on the surface of the hole transport layer 20 close to the perovskite active layer 30, and the preparation process of the functional layer 70 includes: mixing a benzophenone ultraviolet absorber with a first solvent to obtain a first mixed solution, and mixing the first solvent with the second solvent. A mixed liquid is coated on the conductive surface of the transparent conductive substrate 10, or on the surface of the hole transport layer 20 close to the perovskite active layer 30, and is heat-treated to obtain the functional layer 70; and / or, the preparation process of the above-mentioned perovskite active layer 30 includes: mixing a perovskite active material precursor, or a mixture of a dibenzophenone ultraviolet absorber and a perovskite active material precursor with a second solvent to obtain a second mixed liquid, coating the second mixed liquid on the surface of the hole transport layer 20 away from the transparent conductive substrate 10, and obtaining the perovskite active layer 30 after annealing.
[0050] The above-mentioned preparation method enables the benzophenone-based UV absorber to be incorporated into the layer structure of the perovskite solar cell, thereby enhancing its UV absorption effect, helping to inhibit the degradation of the perovskite active material by UV light, and thereby improving the stability of the perovskite solar cell. Furthermore, the above-mentioned preparation method is simple and low-cost. The above-mentioned method enables the benzophenone-based UV absorber to be incorporated into the perovskite active layer 30, facilitating its UV absorption effect and helping to inhibit the degradation of the perovskite active material by UV light, thereby improving the stability of the perovskite solar cell. Furthermore, the above-mentioned preparation method is simple and low-cost.
[0051] In a preferred embodiment, the heat treatment temperature is 100-150°C, and the time is 10-15 minutes. The heat treatment temperature and time include, but are not limited to, the above ranges. Limiting them to the above ranges is beneficial for improving the crystallization quality of the light-absorbing layer and enhancing the interaction between the ultraviolet absorber and the perovskite active layer 30, thereby better suppressing the degradation of the perovskite active material by ultraviolet light, thereby further improving the stability of the perovskite solar cell.
[0052] In a preferred embodiment, the first mixed liquid is applied by spin coating, preferably at a spin coating speed of 2000-5000 rpm and a spin coating time of 20-50 seconds. The spin coating speed and spin coating time include, but are not limited to, the aforementioned ranges. Limiting them to the aforementioned ranges is beneficial for improving the uniformity of the distribution of the first mixed liquid on the surface of the hole transport layer 20, thereby making the thickness of the subsequently prepared perovskite active layer 30 more uniform and maintaining consistent properties across the various regions of the layer.
[0053] In a preferred embodiment, the first solvent includes, but is not limited to, one or more of the group consisting of DMF, DMSO, and gamma-butyrolactone (GBL). Compared to other solvents, the use of these first solvents improves the dispersibility of the benzophenone-based UV absorber, thereby enhancing its UV absorption and, consequently, improving the stability of the perovskite solar cell.
[0054] In a preferred embodiment, during the preparation of the perovskite active layer 30, the annealing temperature is 100-150°C and the duration is 10-15 minutes. The annealing temperature and duration include, but are not limited to, the aforementioned ranges. Limiting the annealing temperature and duration within these ranges is beneficial for improving the film-forming properties of the perovskite active layer 30 and inhibiting cracking. Furthermore, the benzophenone-based UV absorber can be used to inhibit ion migration in the perovskite film, thereby enhancing charge transport at the perovskite grain boundaries and improving the stability of the perovskite solar cell.
[0055] In a preferred embodiment, the second mixed liquid is applied by spin coating, preferably first at a speed of 1000-2000 rpm for 10-40 seconds, and then at a speed of 4000-6000 rpm for 10-20 seconds. The spin coating speed and time include, but are not limited to, the aforementioned ranges. Limiting these ranges helps improve the uniformity of the second mixed liquid distribution on the surface of the hole transport layer 20, thereby making the thickness of the subsequently produced perovskite active layer 30 more uniform, maintaining consistent properties across the layer, and facilitating the effectiveness of the benzophenone-based UV absorber.
[0056] In a preferred embodiment, the second solvent includes but is not limited to one or more of the group consisting of DMF, DMSO and GBL. Compared with other types, the use of the above-mentioned second solvents is beneficial to improving the dispersion uniformity of the perovskite active material and the dibenzophenone ultraviolet absorber therein, and is beneficial to improving the distribution uniformity of the first mixed liquid on the surface of the hole transport layer 20, so that the thickness of the subsequently prepared perovskite active layer 30 is more uniform, thereby better exerting the absorption effect of ultraviolet light.
[0057] In order to further improve the dispersion uniformity of the perovskite active material and the benzophenone ultraviolet absorber, preferably, the first solvent is a mixed solvent of DMF and DMSO.
[0058] The present application has no particular limitation on the type of transparent conductive substrate 10, as long as it is conductive and has high light transmittance. In a preferred embodiment, the transparent conductive substrate 10 includes but is not limited to one or more of the group consisting of ITO conductive glass, IZO conductive glass, and FTO conductive glass.
[0059] In a preferred embodiment, the material of the hole transport layer 20 is one or more selected from the group consisting of, but not limited to, 2PACz ((2-(9H-carbazol-9-yl)ethyl)phosphonic acid), MeO-2PACz ((2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl)phosphonic acid), and Me-4PACz ((4-(3,6-dimethyl-9H-carbazol-9-yl)butyl)phosphonic acid); and the perovskite active material is one or more selected from the group consisting of, but not limited to, ABX3, wherein A includes, but not limited to, CH3NH3. + 、NH=CHNH3 + 、Cs + , B includes but is not limited to Pb 2+ 、Sn 2+ , X includes but is not limited to Cl, Br, and I. Compared with other types, the use of the above-mentioned hole transport materials is beneficial to improving the photoelectric conversion efficiency of perovskite solar cells.
[0060] In a preferred embodiment, the material of the electron transport layer 40 includes, but is not limited to, one or more of the group consisting of PCBM and C60. Compared with other types, the use of the above-mentioned types of electron transport materials is conducive to improving the photoelectric conversion efficiency of the perovskite solar cell.
[0061] In a preferred embodiment, the material of the interface layer 50 includes, but is not limited to, BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) and / or SnO2. Compared to other materials, the use of the above-mentioned interface layer 50 facilitates the preparation of a thinner interface layer 50, which helps reduce damage to the interface layer 50 during the subsequent preparation of the metal electrode layer 60, thereby improving the efficiency and stability of the perovskite solar cell.
[0062] In a preferred embodiment, the material of the metal electrode layer 60 includes, but is not limited to, one or more of the group consisting of Ag, Cu, Au, and Al.
[0063] A third aspect of the present application further provides a photovoltaic module comprising the perovskite solar cell provided herein. The perovskite solar cell provided herein is resistant to ultraviolet degradation and exhibits excellent stability, and its use in a photovoltaic module can extend the service life of the photovoltaic module.
[0064] The present application is further described in detail below with reference to specific embodiments. These embodiments should not be construed as limiting the scope of protection claimed in this application.
[0065] Example 1
[0066] A method for preparing a perovskite solar cell, comprising:
[0067] (1) The ITO conductive glass was ultrasonically cleaned for 15 min using detergent water, deionized water, acetone, and isopropyl alcohol solution, respectively, and dried for later use. The cleaned ITO conductive glass was then plasma treated for 10 min for later use;
[0068] (2) Preparation of hole transport layer 20:
[0069] A 1 mg / mL 2PACz ethanol solution was spin-coated on the ITO at 5000 rpm for 30 seconds, and then dried at 100°C for 10 minutes to obtain a hole transport layer 20 with a thickness of 1.0 nm.
[0070] (3) Preparation of perovskite active layer 30:
[0071] A perovskite precursor solution was prepared using a mixed solvent of 22 mg CsI, 520 mg PbI2, 210 mg PbBr2, 230 mg FAI, 30 mg MABr, 10 mg MACl, DMF and DMSO, and then 10 mg compound 16 ( CAS: 10055-40-0), after being evenly mixed, a perovskite active layer 30 was prepared by spin coating, first at a speed of 2000 rpm for 30 seconds, and then at a speed of 5000 rpm for 20 seconds; 15 seconds before the end of the spin coating process, 200 μL of chlorobenzene was dropped into the center of the substrate. After the spin coating process stopped, the substrate was immediately transferred to a hot plate at 100°C and annealed for 15 minutes to obtain a perovskite active layer 30 with a thickness of 560 nm;
[0072] (4) Preparation of electron transport layer 40:
[0073] Using a spin coating process, a 15 mg / mL chlorobenzene solution of PCBM was deposited on the perovskite active layer 30 at a speed of 2500 rpm for 30 seconds to obtain an electron transport layer 40 with a thickness of 40 nm.
[0074] (5) Preparation of interface layer 50:
[0075] The BCP layer was deposited on the PCBM by spin coating at a speed of 4000 rpm for 30 seconds to obtain an interface layer 50 with a thickness of 7 nm.
[0076] (6) Preparation of metal electrode layer 60:
[0077] A 100 nm thick Ag electrode was deposited on the surface of the BCP film using a vacuum thermal deposition method.
[0078] The effective area of the perovskite solar cell prepared in this embodiment was measured to be 4 mm 2 , and its laminated structure is as follows Figure 1 shown.
[0079] Example 2
[0080] The difference from Example 1 is that the amount of compound 16 is changed so that the weight percentage of compound 16 in the prepared perovskite active layer 30 is 0.5 wt %. The remaining steps are the same as in Example 1.
[0081] Example 3
[0082] The difference from Example 1 is that the amount of compound 16 is changed so that the weight percentage of compound 16 in the prepared perovskite active layer 30 is 5.0 wt %. The remaining steps are the same as in Example 1.
[0083] Example 4
[0084] The difference from Example 1 is that the amount of compound 16 is changed so that the weight percentage of compound 16 in the prepared perovskite active layer 30 is 6 wt %. The remaining steps are the same as in Example 1.
[0085] Example 5
[0086] The difference from Example 1 is that in step (3), 10 mg of compound 1 ( CAS: 611-94-9), to obtain a perovskite active layer 30 doped with compound 1. The remaining steps are the same as in Example 1.
[0087] Example 6
[0088] The difference from Example 1 is that in step (3), 10 mg of compound 2 ( CAS: 131-57-7), to obtain a perovskite active layer 30 doped with compound 2. The remaining steps are the same as in Example 1.
[0089] Example 7
[0090] The difference from Example 1 is that in step (3), 10 mg of compound 3 ( CAS: 13047-06-8), to obtain a perovskite active layer 30 doped with compound 3. The remaining steps are the same as in Example 1.
[0091] Example 8
[0092] The difference from Example 1 is that in step (3), 10 mg of compound 7 ( CAS: 134-84-9), to obtain a perovskite active layer 30 doped with compound 7. The remaining steps are the same as in Example 1.
[0093] Example 9
[0094] The difference from Example 1 is that in step (3), 10 mg of compound 9 ( CAS: 90-93-7), to obtain a perovskite active layer 30 doped with compound 9. The remaining steps are the same as in Example 1.
[0095] Example 10
[0096] The difference from Example 1 is that in step (3), 10 mg of compound 11 ( CAS: 728-86-9), to obtain a perovskite active layer 30 doped with compound 11. The remaining steps are the same as in Example 1.
[0097] Example 11
[0098] The difference from Example 1 is that in step (3), 10 mg of compound 13 ( CAS: 13020-57-0), to obtain a perovskite active layer 30 doped with compound 13. The remaining steps are the same as in Example 1.
[0099] Example 12
[0100] The difference from Example 1 is that the annealing temperature in step (3) is 100° C. and the time is 10 minutes.
[0101] Example 13
[0102] The difference from Example 1 is that the annealing temperature in step (3) is 150° C. and the time is 15 minutes.
[0103] Example 14
[0104] The difference from Example 1 is that the temperature of the annealing treatment in step (3) is 160°C.
[0105] Example 15
[0106] The difference from Example 1 is that compound 16 is not added in step (3); in this example, compound 16 is mixed with DMF and GBL to obtain a first mixed solution, which is spin-coated at a speed of 2000 rpm for 50 seconds to coat the conductive surface of the transparent conductive substrate 10, and then heat-treated at 100°C for 10 minutes to obtain a functional layer 70. The remaining steps are the same as in Example 1. The obtained laminated structure of the perovskite solar cell is as follows: Figure 2 shown.
[0107] Example 16
[0108] The difference from Example 1 is that compound 16 is not added in step (3); in this example, compound 16 is mixed with DMF and GBL to obtain a first mixed solution, which is spin-coated at a speed of 5000 rpm for 20 seconds to coat the surface of the hole transport layer 20 close to the perovskite active layer 30, and then heat-treated at 100°C for 10 minutes to obtain a functional layer 70. The remaining steps are the same as in Example 1. The obtained laminated structure of the perovskite solar cell is as follows: Figure 3 shown.
[0109] Comparative Example 1
[0110] The difference from Example 1 is that no benzophenone ultraviolet absorber compound 16 is added in step (3), and the remaining steps are the same as Example 1. The structure of the obtained perovskite solar cell is as follows: Figure 1 shown.
[0111] The photovoltaic performance test of the perovskite solar cell devices prepared in all the above embodiments and comparative examples of this application was carried out, and the effective area of the devices was 4mm 2; Test conditions are as follows: spectral distribution AM1.5G, light intensity 100mW / cm 2 The JV curves were measured using an AAA solar simulator (Keithley Instruments, Inc., USA). All components were simply packaged with UV adhesive and measured in an atmospheric environment. The results are shown in Table 1 below.
[0112] Table 1
[0113]
[0114] From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects: In the perovskite solar cell provided by the present application, between the transparent conductive substrate 10 and the hole transport layer 20 (such as Figure 2 ), or between the hole transport layer 20 and the perovskite active layer 30 (as shown Figure 3 As shown in the figure, a functional layer 70 with a specific composition is provided. When sunlight irradiates the cell, the benzophenone ultraviolet absorber of the functional layer 70 can absorb ultraviolet light, so that the ultraviolet light is absorbed before it enters the perovskite active layer 30, thereby inhibiting the degradation of the perovskite active material by ultraviolet light and improving the stability of the perovskite solar cell. When the above-mentioned benzophenone ultraviolet absorber is used together with the perovskite active material as the material of the perovskite active layer 30, the benzophenone ultraviolet absorber can passivate the perovskite lattice and surface defects, inhibiting the Pb in the perovskite active material. 2+ It is converted into Pb, which can inhibit ultraviolet degradation, inhibit ion migration in perovskite films, and improve charge transfer at perovskite grain boundaries, thereby significantly improving the stability of perovskite solar cells.
[0115] It should be noted that the terms "first," "second," and the like in the specification and claims of this application are used to distinguish similar objects, and are not necessarily used to describe a specific order or precedence. It should be understood that the terms used in this manner are interchangeable where appropriate, so that the embodiments of the application described herein can, for example, be implemented in an order other than that described herein.
[0116] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention are intended to be within the scope of protection of the present invention.
Claims
1. A perovskite solar cell, comprising a transparent conductive substrate (10), a hole transport layer (20), a perovskite active layer (30), an electron transport layer (40), an interface layer (50) and a metal electrode layer (60) arranged in a stacked manner; It is characterized by: The perovskite solar cell further comprises a functional layer (70), the functional layer (70) being arranged between the transparent conductive substrate (10) and the hole transport layer (20), or between the hole transport layer (20) and the perovskite active layer (30), the material of the functional layer (70) being a benzophenone ultraviolet absorber; and / or the material of the perovskite active layer (30) being a perovskite active material, or being a mixture of a benzophenone ultraviolet absorber and a perovskite active material; The benzophenone ultraviolet absorber has a structure shown in the general formula (I): R1 and R1' are each independently selected from hydrogen or -OH; R2 and R2' are independently selected from hydrogen, -COOH, -OH or C1-C5 alkoxy; R3 and R3' are independently selected from hydrogen, -OH, C1-C5 alkoxy, C1-C5 alkyl, halogen, C1-C5 haloalkyl, cyano, amino, 1 or 2 C2-C5 alkyl-substituted amines, C2-C5 alkyl-substituted amides, or a C1-C5 alkyl-substituted mercapto group; R4 and R4' are each independently selected from hydrogen or -OH; R5 and R5' are independently selected from hydrogen, -OH or halogen; or, R5 and R5' are linked to form -C(=O)- or -S-.
2. The perovskite solar cell according to claim 1, characterized in that Said R2 and said R2' are both hydrogen, or one of them is -COOH and the other is hydrogen, or one of them is -OH and the other is hydrogen, or one of them is methoxy and the other is hydrogen; said R3 and said R3' are independently selected from hydrogen, -OH, methoxy, methyl, fluorine, chlorine, cyano, amino, or methylthio; one of said R4 and said R4' is -OH and the other is hydrogen, or both are hydrogen; said R5 and said R5' are independently selected from hydrogen, -OH, bromine or chlorine.
3. The perovskite solar cell according to claim 1, wherein The benzophenone ultraviolet absorber is selected from any one or more of the following structures:
4. The perovskite solar cell according to any one of claims 1 to 3, characterized in that When the material of the perovskite active layer (30) is a mixture of the benzophenone ultraviolet absorber and the perovskite active material, the weight percentage of the benzophenone ultraviolet absorber is 0.5 to 5.0 wt % based on the total weight of the perovskite active layer (30).
5. The perovskite solar cell according to any one of claims 1 to 3, characterized in that The thickness of the functional layer (70) is 10-100 nm.
6. A method for preparing a perovskite solar cell according to any one of claims 1 to 5, comprising sequentially preparing a hole transport layer (20), a perovskite active layer (30), an electron transport layer (40), an interface layer (50) and a metal electrode layer (60) on the conductive surface side of a transparent conductive substrate (10); It is characterized by: The preparation method further comprises preparing a functional layer (70) on the conductive surface side of the transparent conductive substrate (10) or on the surface of the hole transport layer (20) close to the perovskite active layer (30), wherein the preparation process of the functional layer (70) comprises: mixing a benzophenone ultraviolet absorber with a first solvent to obtain a first mixed liquid, coating the first mixed liquid on the conductive surface side of the transparent conductive substrate (10) or on the surface of the hole transport layer (20) close to the perovskite active layer (30), and heat-treating to obtain the functional layer (70); and / or, The preparation process of the perovskite active layer (30) comprises: mixing a perovskite active material precursor, or a mixture of a benzophenone ultraviolet absorber and a perovskite active material precursor, with a second solvent to obtain a second mixed liquid; coating the second mixed liquid on a surface of the hole transport layer (20) away from the transparent conductive substrate (10); and performing an annealing treatment to obtain the perovskite active layer (30).
7. The method for preparing a perovskite solar cell according to claim 6, wherein: During the preparation of the functional layer (70), the heat treatment temperature is 100-150° C. and the time is 10-15 minutes; and / or, The first mixed solution is coated by spin coating, preferably with a spin coating speed of 2000 to 5000 rpm and a spin coating time of 20 to 50 s; and / or, The first solvent is selected from one or more of the group consisting of DMF, DMSO and γ-butyrolactone.
8. The method for preparing a perovskite solar cell according to claim 6, wherein: During the preparation of the perovskite active layer (30), the annealing treatment is performed at a temperature of 100 to 150° C. and for a time of 10 to 15 minutes; and / or The second mixed solution is applied by spin coating, preferably firstly at a rotation speed of 1000-2000 rpm for 10-40 seconds, and then at a rotation speed of 4000-6000 rpm for 10-20 seconds; and / or, The second solvent is selected from one or more of the group consisting of DMF, DMSO and γ-butyrolactone, and is preferably a mixed solvent of DMF and DMSO.
9. The method for preparing a perovskite solar cell according to any one of claims 6 to 8, characterized in that: The perovskite active material precursor is selected from one or more of the group consisting of FAPbI3, MAPbI3, FAPbBr3, MAPbBr3, CsBr and CsI.
10. A photovoltaic module, characterized in that: The photovoltaic module comprises the perovskite solar cell according to any one of claims 1 to 5.