Interface modified perovskite device and preparation method thereof
By introducing a metal fluoride layer into the perovskite solar cell to improve the interface quality, the stability problem of the perovskite solar cell was solved, and the stability and photoelectric conversion efficiency of the device were improved.
Patent Information
- Application Number
- CN202410495257.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-04-23
- Publication Date
- 2025-10-24
AI Technical Summary
The stability issues of perovskite solar cells are mainly caused by the poor interface quality between the hole transport material nickel oxide and the halide perovskite, which affects the device performance and stability.
A metal fluoride layer, including fluorides of lanthanides and group IVB elements, is disposed between the hole transport layer and the perovskite layer. The preferred fluorides are zirconium fluoride, lanthanum fluoride, etc., with a thickness of 1~5 nm, to improve the interface quality and block the migration of iodine ions.
It improves the stability and photoelectric conversion efficiency of perovskite solar cells and reduces the rate of performance degradation, especially when operating under standard light for extended periods.
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Figure CN120835668A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of perovskite batteries, and particularly relates to an interface modified perovskite device and a preparation method thereof. BACKGROUND
[0002] Perovskite solar cells are a new type of solar cell, which uses perovskite crystals as a photoelectric conversion layer to directly convert solar energy into electricity, and is a new green energy that is expected to change global energy supply. In theory, perovskite solar cells have good photoelectric conversion efficiency, and are more likely to achieve the goal of low energy consumption and sustainability due to their portability, ease of production and low cost.
[0003] Currently, perovskite solar cells mainly include single-junction perovskite solar cells and stacked perovskite solar cells. Among them, single-junction perovskite solar cells are the basis of all perovskite solar cell product forms, and have relatively lower technical difficulty, with a theoretical conversion efficiency of 33%, and the highest certified efficiency in the laboratory is currently 25.8%. In recent years, the efficiency of single-junction perovskite solar cells has been continuously improved, and the efficiency of commercial silicon-based solar cells has gradually approached its theoretical limit, indicating a new direction for the development of the photovoltaic industry.
[0004] However, the stability problem of perovskite has been affecting the progress of commercialization of perovskite solar cells. As a commonly used hole transport material for transverse perovskite solar cells, nickel oxide has a poor interface quality with halide perovskite, which limits the performance and stability of perovskite solar cells based on nickel oxide. Therefore, lithium fluoride and magnesium fluoride are widely used for interface modification of the hydrophobic transport layer to obtain high-quality perovskite film layers. However, the running stability of perovskite solar cells using lithium fluoride to modify the hydrophobic transport layer is still not ideal. The displacement of ions or charge defects in the perovskite layer is considered to be the main reason for the performance degradation of the device in the working environment of electric field, heat and excess charge carriers. Therefore, the running stability of perovskite solar cells depends largely on the inhibition of ion migration. SUMMARY
[0005] Therefore, the technical problem to be solved by the present application is to provide an interface modified perovskite device with high stability and a preparation method thereof.
[0006] The present application provides an interface modified perovskite device, comprising a hole transport layer and a perovskite layer; a metal fluoride layer is arranged between the hole transport layer and the perovskite layer.
[0007] The metal fluoride layer comprises one or more of a fluoride of a lanthanide element and a fluoride of a group IVB element.
[0008] Preferably, the metal fluoride layer comprises one or more of zirconium fluoride, lanthanum fluoride and dysprosium fluoride.
[0009] Preferably, the metal fluoride layer has a thickness of 1-5 nm.
[0010] Preferably, the perovskite layer comprises A 1-x Cs x BX3; wherein x is 0.1-0.2; A is MA + and / or FA + ; B is Pb 2+ and / or Sn 2+ ; X is one or more of I - , Br - and Cl - .
[0011] Preferably, the hole transport layer comprises one or more of nickel oxide, cuprous thiocyanate, cuprous iodide, copper oxide and graphene oxide.
[0012] Preferably, the hole transport layer has a thickness of 10-20 nm.
[0013] The perovskite layer has a thickness of 100-500 nm.
[0014] Preferably, the perovskite device comprises, in sequence, a transparent conductive substrate, a hole transport layer, a metal fluoride layer, a perovskite layer, an electron transport layer and a metal electrode.
[0015] Preferably, the electron transport layer comprises fullerene and / or a fullerene derivative.
[0016] Preferably, the electron transport layer has a thickness of 15-30 nm.
[0017] Preferably, a hole blocking layer is further provided between the electron transport layer and the metal electrode.
[0018] The hole blocking layer has a thickness of 5-15 nm.
[0019] The present application also provides a method for preparing an interface-modified perovskite device, comprising the following steps:
[0020] S1) forming a hole transport layer on the surface of a transparent conductive substrate;
[0021] S2) forming a metal fluoride layer on the surface of the hole transport layer; the metal fluoride layer comprises one or more of a fluoride of a lanthanide element and a fluoride of an element of group IVB;
[0022] S3) forming a perovskite layer on the surface of the metal fluoride layer;
[0023] S4) forming an electron transport layer on the surface of the perovskite layer;
[0024] S5) forming a metal electrode on the surface of the electron transport layer to obtain an interface-modified perovskite cell.
[0025] The application provides an interface-modified perovskite device, comprising a hole transport layer and a perovskite layer; a metal fluoride layer is arranged between the hole transport layer and the perovskite layer; the metal fluoride layer comprises one or more of a fluoride of a lanthanide element and a fluoride of an element in group IVB. Compared with the prior art, the application can improve the film forming effect of the perovskite layer by arranging a high-valence metal fluoride layer on the hole transport layer, so as to obtain a high-quality perovskite film, and the high-valence metal cation can effectively block the migration of iodine ions, thereby further improving the stability of the perovskite cell. BRIEF DESCRIPTION OF DRAWINGS
[0026] Figure 1 A structure schematic diagram of a perovskite device provided by the application is shown in the figure;
[0027] Figure 2 A preparation flow schematic diagram of an interface-modified perovskite device provided by the application is shown in the figure. DETAILED DESCRIPTION
[0028] The technical solutions in the embodiments of the application will be clearly and completely described below with reference to the embodiments of the application. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments of the application. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the application.
[0029] The application provides an interface-modified perovskite device, comprising a hole transport layer and a perovskite layer; a metal fluoride layer is arranged between the hole transport layer and the perovskite layer; the metal fluoride layer comprises one or more of a fluoride of a lanthanide element and a fluoride of an element in group IVB.
[0030] According to the application, the hole transport layer preferably comprises one or more of nickel oxide, cuprous thiocyanate, cuprous iodide, copper oxide and graphene oxide, more preferably nickel oxide; the thickness of the hole transport layer is preferably 10-20 nm, more preferably 12-18 nm, still more preferably 14-16 nm, and most preferably 15 nm.
[0031] According to the present application, the hole transport layer is provided with a metal fluoride layer; the metal fluoride layer comprises one or more of fluorides of lanthanide elements and fluorides of IVB elements; the IVB elements comprise one or more of titanium, zirconium and hafnium; in the present application, the metal fluoride preferably comprises fluorides of lanthanide metals and / or zirconium fluoride, more preferably one or more of zirconium fluoride, lanthanum fluoride and dysprosium fluoride, and even more preferably lanthanum fluoride and / or zirconium fluoride; the thickness of the metal fluoride layer is preferably 1-5 nm, more preferably 1-4 nm, and even more preferably 1-3 nm; in some embodiments provided by the present application, the thickness of the metal fluoride layer is specifically 1 nm, 2 nm or 3 nm.
[0032] The surface of the metal fluoride layer is provided with a perovskite layer; the perovskite layer can be any halide perovskite material known to those skilled in the art, and is not specifically limited, and in the present application, A 1-x Cs x BX3; wherein x is preferably 0.1-0.2, more preferably 0.12-0.2, even more preferably 0.14-0.2, even more preferably 0.16-0.18, and most preferably 0.17; A is MA + and / or FA + ; B is Pb 2+ and / or Sn 2+ ; X is one or more of I - , Br - and Cl - ; the thickness of the perovskite layer is preferably 100-500 nm.
[0033] According to the present application, the perovskite device can be a single-junction perovskite cell, a stacked perovskite cell, or a perovskite LED, and is not specifically limited; in one specific embodiment provided by the present application, the perovskite device is a single-junction perovskite cell, and specifically the perovskite device comprises, in sequence, a transparent conductive substrate, a hole transport layer, a metal fluoride layer, a perovskite layer, an electron transport layer and a metal electrode. See Figure 1 , Figure 1 for a structural schematic diagram of a perovskite device provided by the present application, wherein 1 is a transparent conductive substrate, 2 is a hole transport layer, 3 is a metal fluoride layer, 4 is a perovskite layer, 5 is an electron transport layer, and 6 is a hole blocking layer.
[0034] The transparent conductive substrate can be any transparent conductive substrate known to those skilled in the art, and is not specifically limited, and in the present application, ITO conductive glass, FTO conductive glass or flexible transparent plastic coated with ITO is preferred.
[0035] The transparent conductive substrate is provided with a hole transport layer; the hole transport layer is as described above, and will not be described here again.
[0036] The metal fluoride layer is provided on the hole transport layer; the metal fluoride layer is as described above, and will not be repeated here.
[0037] The perovskite layer is provided on the metal fluoride layer; the perovskite layer is as described above, and will not be repeated here.
[0038] The electron transport layer is provided on the perovskite layer; the electron transport layer is well known to those skilled in the art, and is not particularly limited, and in the present application, fullerene and / or fullerene derivatives are preferred; the fullerene is preferably C60 and / or C70; the fullerene derivative is preferably PCBM; the thickness of the electron transport layer is preferably 15-30 nm.
[0039] The metal electrode is provided on the electron transport layer; the metal electrode is well known to those skilled in the art, and is not particularly limited, and in the present application, one or more of a copper electrode, a gold electrode and a silver electrode is preferred; the thickness of the metal electrode is preferably 10-500 nm.
[0040] In another specific embodiment provided by the present application, a hole blocking layer is preferably further provided between the electron transport layer and the metal electrode; the hole blocking layer is well known to those skilled in the art, and is not particularly limited, and in the present application, one or more of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi), aluminum zinc oxide (AZO) and zirconium acetate (Zr(AC)4) is preferred; the thickness of the hole blocking layer is preferably 5-15 nm, more preferably 8-12 nm, and even more preferably 10 nm.
[0041] The present application also provides a preparation method of the interface-modified perovskite device, comprising the following steps: forming a metal fluoride layer on the surface of the hole transport layer, and then forming a perovskite layer on the surface of the metal fluoride.
[0042] Referring to Figure 2 , Figure 2 The present application provides a preparation flowchart of the interface-modified perovskite device.
[0043] Among them, the present application does not have special restrictions on the source of all raw materials, which can be purchased on the market.
[0044] In one specific embodiment of the present application, the method for preparing the interface-modified perovskite device comprises the following steps: S1) forming a hole transport layer on the surface of a transparent conductive substrate; S2) forming a metal fluoride layer on the surface of the hole transport layer; the metal fluoride layer comprises one or more of a fluoride of a lanthanide element and a fluoride of an element of Group IVB; S3) forming a perovskite layer on the surface of the metal fluoride layer; S4) forming an electron transport layer on the surface of the perovskite layer; S5) forming a metal electrode on the surface of the electron transport layer to obtain an interface-modified perovskite cell.
[0045] The method for forming each layer in the present application can be a physical deposition method and / or a chemical deposition method known to those skilled in the art, and is not particularly limited. The physical deposition method includes, but is not limited to, vacuum evaporation, sputtering, ion beam deposition, pulsed laser deposition, etc.; the chemical deposition method includes, but is not limited to, chemical vapor deposition, atomic layer deposition, sol-gel spin coating, etc.
[0046] According to the present application, further specifically, the transparent conductive substrate is preferably cleaned and subjected to ultraviolet ozone treatment before the hole transport layer is formed on the surface thereof; the method for forming the hole transport layer can be any method known to those skilled in the art, and is not particularly limited, and in the present application, the method of sputtering is preferably used; the hole transport layer is as described above, and will not be repeated here.
[0047] The metal fluoride layer is formed on the surface of the hole transport layer; the method for forming the metal fluoride layer can be any method known to those skilled in the art, and is not particularly limited, and in the present application, thermal evaporation is preferably used; the rate of thermal evaporation is preferably 2-5 Å / s, and more preferably 2-3 Å / s; the metal fluoride layer is as described above, and will not be repeated here.
[0048] The perovskite layer is formed on the surface of the metal fluoride layer; the perovskite layer is as described above, and will not be repeated here; specifically, a perovskite material solution is spin-coated onto the surface of the metal fluoride layer, then a reverse solvent is spin-coated, and a perovskite layer is formed after annealing; the perovskite material solution comprises AX, CsX and BX2; A is MA + and / or FA + ; B is Pb 2+ and / or Sn 2+ ; X is I - , Br - and Cl -one or more of the following: AX, CsX, and BX2; the molar ratio of AX, CsX, and BX2is preferably 1-x:x:1; x is preferably 0.1-0.2, more preferably 0.12-0.2, even more preferably 0.14-0.2, yet more preferably 0.16-0.18, most preferably 0.17; further specifically, BX2is preferably BI2and BBr2; the molar ratio of BI2and BBr2is preferably 1-y:y; y is preferably 0.1-0.2, more preferably 0.12-0.18, even more preferably 0.14-0.16, most preferably 0.15; the molar ratio of BX2in the perovskite material solution is preferably 1-2 mol / L, more preferably 1.3-1.8 mol / L, even more preferably 1.5 mol / L; the solvent of the perovskite material solution can be any organic solvent known to one skilled in the art without special limitation, and in the present application, N,N-dimethylformamide (DMF) and / or dimethyl sulfoxide (DMSO) are preferred, more preferably N,N-dimethylformamide and dimethyl sulfoxide; the volume ratio of N,N-dimethylformamide and dimethyl sulfoxide is preferably (2-6):1, more preferably (3-5):1, even more preferably 4:1; the volume of the spin-coated perovskite material solution is preferably 50-200 microliters, more preferably 50-150 microliters, even more preferably 80-100 microliters; the method of spin-coating can be any method known to one skilled in the art without special limitation, and in the present application, stepwise spin-coating, more preferably two-step spin-coating, is preferred; the rotation speed of the first step of two-step spin-coating is preferably 500-1500 rpm, more preferably 800-1200 rpm, even more preferably 1000 rpm; the time of the first step of spin-coating is preferably 5-15 s, more preferably 8-12 s, even more preferably 10 s; the rotation speed of the second step of two-step spin-coating is preferably 3000-6000 rpm, more preferably 4000-5500 rpm, even more preferably 5000 rpm; the time of the second step of spin-coating is preferably 20-40 s, more preferably 25-35 s, even more preferably 30 s; the anti-solvent can be any anti-solvent known to one skilled in the art without special limitation, and in the present application, anisole is preferred; the anti-solvent is preferably added 5-15 s before the end of the second step of spin-coating, more preferably 10 s before the end of the second step of spin-coating; the annealing temperature is preferably 120°C-200°C, more preferably 140°C-180°C, even more preferably 150°C-160°C; the annealing time is preferably 5-30 min, more preferably 7-20 min, even more preferably 9-15 min, most preferably 10 min.
[0049] An electron transport layer is formed on the surface of the perovskite layer; the electron transport layer is the same as described above, and will not be repeated here; the method for forming the electron transport layer can be any method known to one skilled in the art, and is not particularly limited, and in the present application, spin coating is preferred; specifically, a solution containing an electron transport material is spin coated onto the surface of the perovite layer; the electron transport material can be any electron transport material known to one skilled in the art, and is not particularly limited, and in the present application, fullerene and / or a fullerene derivative are preferred; the fullerene is preferably C60 and / or C70; the fullerene derivative is preferably PCBM; the solvent of the solution containing the electron transport material can be any organic solvent known to one skilled in the art, and is not particularly limited, and in the present application, chlorobenzene is preferred; the concentration of the electron transport material in the solution containing the electron transport material is preferably 10-30 mg / mL, more preferably 15-25 mg / mL, and even more preferably 20 mg / mL; the volume of the solution containing the electron transport material that is spin coated is preferably 50-100 microliters, more preferably 50-80 microliters, and even more preferably 60 microliters; the spin coating speed is preferably 1000-3000 rpm, more preferably 1500-2500 rpm, and even more preferably 2000 rpm; the spin coating time is preferably 20-60 s, more preferably 30-50 s, and even more preferably 40 s.
[0050] A metal electrode is formed on the surface of the electron transport layer to obtain an interface-modified perovskite battery; the metal electrode is the same as described above, and will not be repeated here; the method for forming the metal electrode can be any method known to one skilled in the art, and is not particularly limited, and in the present application, evaporation is preferred.
[0051] In another specific embodiment provided by the present application, a hole blocking layer is preferably formed on the surface of the electron transport layer, and then a metal electrode is formed on the surface of the hole blocking layer; the type and thickness of the hole blocking layer are the same as described above, and will not be repeated here; the method for forming the hole blocking layer can be any method known to one skilled in the art, and is not particularly limited, and in the present application, evaporation is preferred; the evaporation rate is preferably 0.5-2 Å / s.
[0052] In order to further illustrate the present application, the present application provides an interface-modified perovskite battery and a preparation method thereof, which are described in detail below with reference to the examples.
[0053] The reagents used in the following examples are all commercially available.
[0054] Example 1.
[0055] Step (1): ITO conductive glass substrate cleaning, ultraviolet ozone treatment;
[0056] Step (2): A nickel oxide hole transport layer was prepared on the ITO conductive glass by sputtering method, with a thickness of 15 nm;
[0057] Step (3): A layer of lanthanum fluoride was prepared on the nickel oxide hole transport layer by evaporation method, with an evaporation rate of 2 Å / s and a thickness of 1 nm;
[0058] Step (4): Cesium iodide (CsI), formamidinium iodide (FAI), lead iodide (PbI2) and lead bromide (PbBr2) were dissolved in a mixed solvent of N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) at a molar ratio of 0.17:0.83:0.85:0.15, with a solvent volume ratio of DMF:DMSO being 4:1, and the concentration of the obtained perovskite solution was 1.5 M;
[0059] Step (5): 80 microliters of the perovskite solution was distributed and spin-coated onto the lanthanum fluoride layer, first at 1000 rpm for 10 s, then at 5000 rpm for 30 s, and finally 300 microliters of anti-solvent anisole was added dropwise at 10 s, followed by annealing at 150°C for 10 min and cooling to room temperature, to obtain a perovskite layer;
[0060] Step (6): PCBM was dissolved in chlorobenzene to prepare a PCBM solution with a concentration of 20 mg / mL;
[0061] Step (7): 60 microliters of the PCBM solution was spin-coated onto the perovskite layer at 2000 rpm for 40 s;
[0062] Step (8): A layer of BCP film was prepared on the top of PCBM by evaporation method, with an evaporation rate of 0.5 Å / s and a thickness of 10 nm;
[0063] Step (9): A silver metal electrode was prepared on the BCP by evaporation through a mask, with a thickness of 100 nm, to obtain a perovskite cell.
[0064] Example 2.
[0065] The same steps as steps (1)-(2), (4)-(9) in Example 1 were adopted, and the thickness of the lanthanum fluoride layer in step (3) was changed to 2 nm.
[0066] Example 3.
[0067] The same steps as steps (1)-(2), (4)-(9) in Example 1 were adopted, and the thickness of the lanthanum fluoride layer in step (3) was changed to 3 nm.
[0068] Example 4.
[0069] The same steps as steps (1) to (2) and (4) to (9) in Example 1 were used, except that lanthanum fluoride in step (3) was replaced by zirconium fluoride and the thickness was changed to 2 nm.
[0070] Comparative Example 1.
[0071] The same steps as steps (1) to (2) and (4) to (9) in Example 1 were used, except that lanthanum fluoride in step (3) was replaced by lithium fluoride and the thickness was changed to 1 nm.
[0072] Comparative Example 2.
[0073] The same steps as steps (1) to (2) and (4) to (9) in Example 1 are adopted, and step (3) is removed.
[0074] The fabricated perovskite battery was tested, and the Eff (photoelectric conversion efficiency) of the battery was measured using a steady-state light source IV tester. The test results are shown in Table 1.
[0075] Table 1 Performance test results of perovskite cells
[0076] The prepared perovskite cell was continuously operated for 240 h under standard light, and the Eff (photoelectric conversion efficiency) of the cell was measured using a steady-state light source IV tester. The test results are shown in Table 2.
[0077] Table 2 Performance test results of perovskite cells
[0078] As can be seen from Table 1, the performance of the perovskite battery prepared in Example 1 and Comparative Example 1 with thinner metal fluoride-modified hole transport layers is slightly better than that in Comparative Example 2 with unmodified hole transport layers. After the metal fluoride modification is thickened in Examples 2 to 4, the performance of the battery device decreases as the thickness of the metal fluoride increases.
[0079] As can be seen from Table 2, after 240 hours of continuous operation under standard light, compared with the batteries modified with different thicknesses of metal fluorides in Examples 1 to 3, the photoelectric conversion efficiency of Example 1 decreased by 20%, the photoelectric conversion efficiency of Example 2 decreased by 13%, and the photoelectric conversion efficiency of Example 3 decreased by 10%, indicating that increasing the thickness of the metal fluoride enhances the stability of the battery device. Example 4 uses different metal fluorides, and the photoelectric conversion efficiency decreases by 13%. Comparative Example 1 uses low-priced lithium fluoride modification, and the photoelectric conversion efficiency decreases by 31%, which is significantly inferior to the batteries of Examples 1 to 4 using high-priced metal fluorides. The battery of Comparative Example 2 is not modified, and the photoelectric conversion efficiency decreases by 49%.
[0080] The above disclosed preferred embodiments of the present application are only used to help explain the present application, but the present application is not limited thereto. Those skilled in the art can understand that within the technical concept scope of the present application, the technical solutions of the present application can be modified, or some technical features can be combined in any other way. These modifications or combinations do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application, and should be considered as the disclosed content of the present application, and all belong to the protection scope of the present application.
Claims
1. An interface-modified perovskite device, characterized in that, The perovskite device comprises a transparent conductive substrate, a hole transport layer, a metal fluoride layer, a perovskite layer, an electron transport layer and a metal electrode arranged in sequence. The metal fluoride layer comprises one or more of a fluoride of a lanthanide element and a fluoride of an element of group IVB; the element of group IVB comprises one or more of titanium, zirconium and hafnium.
2. The perovskite device of claim 1, wherein, The metal fluoride layer comprises one or more of zirconium fluoride, lanthanum fluoride and dysprosium fluoride.
3. The perovskite device according to claim 1 or 2, wherein The thickness of the metal fluoride layer is 1-5 nm.
4. The perovskite device of claim 1, wherein, The perovskite layer comprises A 1-x Cs x BX3; wherein x is 0.1-0.2; A is MA + and / or FA + ; B is Pb 2+ and / or Sn 2+ ; and X is one or more of I - , Br - , and Cl - .
5. The perovskite device of claim 1, wherein, The hole transport layer comprises one or more of nickel oxide, cuprous thiocyanate, cuprous iodide, copper oxide and graphene oxide.
6. The perovskite device according to claim 1 or 5, wherein, The thickness of the hole transport layer is 10-20 nm. The thickness of the perovskite layer is 100-500 nm.
7. The perovskite device of claim 1, wherein, The perovskite device comprises a transparent conductive substrate, a hole transport layer, a metal fluoride layer, a perovskite layer, an electron transport layer and a metal electrode arranged in sequence.
8. The perovskite device of claim 7, wherein, The electron transport layer comprises fullerene and / or a fullerene derivative. The thickness of the electron transport layer is 15-30 nm.
9. The perovskite device of claim 7, wherein, A hole blocking layer is further arranged between the electron transport layer and the metal electrode. The thickness of the hole blocking layer is 5-15 nm.
10. A method of preparing an interface-modified perovskite device, characterized by, The method comprises the following steps: S1) forming a hole transport layer on the surface of a transparent conductive substrate; S2) forming a metal fluoride layer on the surface of the hole transport layer; the metal fluoride layer comprises one or more of a fluoride of a lanthanide element and a fluoride of an element of group IVB; the element of group IVB comprises one or more of titanium, zirconium and hafnium; S3) forming a perovskite layer on the surface of the metal fluoride layer; S4) forming an electron transport layer on the surface of the perovskite layer; S5) forming a metal electrode on the surface of the electron transport layer to obtain an interface-modified perovskite battery.