Perovskite solar cell and preparation method thereof, preparation method of spinel type metal oxide, and photovoltaic module

Abstract

The embodiment of the invention provides a perovskite solar cell, a preparation method of the perovskite solar cell, a preparation method of spinel type metal oxide and a photovoltaic module. The perovskite solar cell comprises a conversion layer, a transparent glass substrate, a transparent conductive layer, a hole transport layer, a perovskite absorption layer, an electron transport layer and a top electrode which are stacked in sequence, wherein the material of the conversion layer comprises a spinel type metal oxide. According to the technical scheme of the invention, the photoelectric conversion efficiency and ultraviolet stability of the cell can be improved.

Description

Technical Field

[0001] This application relates to the technical field of solar cells, and particularly relates to a perovskite solar cell, a preparation method thereof, a preparation method of a spinel-type metal oxide, and a photovoltaic module. Background Art

[0002] Perovskite solar cells (PSCs) are one of the most disruptive technologies in the photovoltaic field and have rapidly emerged due to their high efficiency, low cost, and flexible potential. Their material properties are excellent and the preparation process is simple. However, the perovskite solar cells (PSCs) have poor ultraviolet stability, mainly due to the sensitivity of their organic-inorganic hybrid structure to ultraviolet light (<400 nm). Ultraviolet light can trigger photocatalytic reactions, resulting in the decomposition of organic components (such as MA + 、FA + ), and the breaking of Pb-I bonds. At the same time, the commonly used electron transport layer generates oxygen vacancies and free radicals under ultraviolet light, exacerbating material degradation. In addition, oxygen and humidity in the environment will accelerate the decomposition of perovskite under ultraviolet light irradiation. To address this problem, some researchers add an ultraviolet filter layer (such as a UV-cut coating or an ultraviolet cut-off film) on the device surface to reduce the incidence of ultraviolet light. However, such methods are only used to block ultraviolet light and cannot effectively utilize ultraviolet light.

[0003] It should be noted that the above content is not necessarily prior art and is not used to limit the patent protection scope of this application. Summary of the Invention

[0004] Embodiments of this application provide a perovskite solar cell, a preparation method thereof, a preparation method of a spinel-type metal oxide, and a photovoltaic module to solve or alleviate the above-mentioned technical problems. The perovskite solar cell of the technical solution of this application can improve the photoelectric conversion efficiency and ultraviolet stability of the battery.

[0005] In a first aspect, embodiments of this application provide a perovskite solar cell, including: A conversion layer, a transparent glass substrate, a transparent conductive layer, a hole transport layer, a perovskite absorption layer, an electron transport layer, and a top electrode that are sequentially stacked; Wherein, the material of the conversion layer includes a spinel-type metal oxide.

[0006] Optionally, the spinel-type metal oxide includes one or more of ZnGa2O4-type materials, ZnIn2O4-type materials, and ZnAl2O4-type materials.

[0007] Optionally, the ZnGa2O4-type material includes ZnGa2O4:Bi 3+ / Mn 4+ 、ZnGa2O4:Eu3+ / Cr 3+ 、ZnGa2O4:Sb 3 + / Fe 3+ 、ZnGa2O4:Pr 3+ / V 5+ one or more of the following.

[0008] Optionally, the ZnIn2O4-based material includes ZnIn2O4:Bi 3+ / Mn 4+ 、ZnIn2O4:Eu 3+ / Cr 3+ 、ZnIn2O4:Sb 3 + / Fe 3+ 、ZnIn2O4:Pr 3+ / V 5+ one or more of the following.

[0009] Optionally, the ZnAl2O4-based material includes ZnAl2O4:Bi 3+ / Mn 4+ 、ZnAl2O4:Eu 3+ / Cr 3+ 、ZnAl2O4:Sb 3 + / Fe 3+ 、ZnAl2O4:Pr 3+ / V 5+ one or more of the following.

[0010] Optionally, the refractive index of the conversion layer is 1.5 - 2.

[0011] Optionally, the thickness of the conversion layer is 50 nm - 100 nm.

[0012] In a second aspect, an embodiment of the present application provides a method for preparing a spinel-type metal oxide for a perovskite solar cell, comprising: Mixing and grinding the raw materials of the spinel-type metal oxide to obtain a mixed powder; Performing a first sintering on the mixed powder in air, wherein the temperature of the first sintering is 350°C - 450°C; Performing a second sintering on the powder after the first sintering, wherein the temperature of the second sintering is 1200°C - 1300°C; Washing the powder after the second sintering with an acid solution to obtain a pickling product; Forming the pickling product into a spinel-type metal oxide by a sol-gel method.

[0013] Optionally, the raw materials of the spinel-type metal oxide include: ZnO, metal oxide M2O3, a first metal salt, and a second metal salt; Among them, M in the metal oxide is selected from one of Ga, In, and Al, the metal in the first metal salt is selected from one of Bi, Eu, Sb, and Pr, and the metal in the second metal salt is selected from one of Mn, Cr, Fe, and V.

[0014] In a third aspect, an embodiment of the present application provides a method for preparing a perovskite solar cell, including: Providing a transparent glass substrate; Successively forming a transparent conductive layer, a hole transport layer, a perovskite absorption layer, an electron transport layer, and a top electrode on the transparent glass substrate; Forming a conversion layer on a side of the transparent glass substrate away from the transparent conductive layer; the material of the conversion layer includes a spinel-type metal oxide.

[0015] Optionally, forming a conversion layer on a side of the transparent glass substrate away from the transparent conductive layer includes: Preparing a conversion layer precursor solution; among them, the conversion layer precursor solution includes the spinel-type metal oxide, an organic solvent, and a dispersant; Coating the conversion layer precursor solution on a side of the transparent glass substrate away from the transparent conductive layer, and after annealing treatment, forming a conversion layer.

[0016] Optionally, the organic solvent includes one or more of ethanol, propanol, and butanol; and / or The dispersant includes one or two of polyvinylpyrrolidone and ammonium citrate.

[0017] In a fourth aspect, an embodiment of the present application provides a photovoltaic module, including: the perovskite solar cell provided in any one of the above embodiments.

[0018] The embodiments of the present application adopting the above technical solutions may include the following advantages: In the perovskite solar cell of the embodiment of the present application, a conversion layer formed of a spinel-type metal oxide is provided on the light incident surface of the transparent glass substrate. The spinel-type metal oxide includes a sensitizer and an activator. The conversion layer can transfer short-wavelength light to the activator through the sensitizer and convert it into light within the perovskite light absorption range, thereby improving the photoelectric conversion efficiency of the perovskite cell, achieving an antireflection effect, and enhancing the ultraviolet stability of the perovskite solar cell. Description of the Drawings

[0019] In the drawings, unless otherwise specified, the same reference numerals throughout the several views denote the same or similar components or elements. These drawings are not necessarily drawn to scale. It should be understood that these drawings depict only some embodiments disclosed in the present application and should not be regarded as limiting the scope of the present application.

[0020] Figure 1 is a schematic structural diagram of a perovskite solar cell provided by an embodiment of the present application.

[0021] Description of reference numerals: 1. Conversion layer; 2. Transparent glass substrate; 3. Transparent conductive layer; 4. Hole transport layer; 5. Perovskite absorption layer; 6. Electron transport layer; 7. Top electrode. Detailed description of the specific implementation

[0022] The embodiments of the present application will be described in detail below, and the examples of the embodiments are shown in the drawings. In the drawings, for clarity, the dimensions of layers, regions, and elements, as well as their relative dimensions, may be exaggerated. Wherever the same or similar reference numerals are used throughout, they denote the same or similar elements or elements having the same or similar functions. The embodiments described below are exemplary and are only used to explain the present application and should not be construed as limiting the present application. It should be noted that, without conflict, the embodiments in the present application and the features in the embodiments may be combined with each other.

[0023] As Figure 1 shown, an embodiment of the present application provides a perovskite solar cell, including: A conversion layer 1, a transparent glass substrate 2, a transparent conductive layer 3, a hole transport layer 4, a perovskite absorption layer 5, an electron transport layer 6, and a top electrode 7 that are sequentially stacked; Among them, the material of the conversion layer 1 includes a spinel-type metal oxide.

[0024] In the perovskite solar cell of the embodiment of the present application, a conversion layer formed of a spinel-type metal oxide is provided on the light incident surface of the transparent glass substrate. The spinel-type metal oxide includes a sensitizer and an activator. The conversion layer can transfer short-wavelength light to the activator through the sensitizer and convert it into light within the perovskite light absorption range, thereby improving the photoelectric conversion efficiency of the perovskite battery, achieving an antireflection effect, and enhancing the ultraviolet stability of the perovskite solar cell.

[0025] In some embodiments, the spinel-type metal oxide includes one or more of ZnGa2O4-type materials, ZnIn2O4-type materials, and ZnAl2O4-type materials.

[0026] These spinel-type metal oxides (ZnGa2O4-type materials, ZnIn2O4-type materials, ZnAl2O4-type materials) have unique optical properties. They can absorb short-wavelength light (such as ultraviolet light) and transfer it to the activator through a sensitizer, converting it into light within the perovskite light absorption range, thereby increasing the number of photons entering the perovskite absorption layer and improving the photoelectric conversion efficiency of the battery. These materials can be used as an antireflection layer to reduce the reflectivity of the surface of the transparent glass substrate, reduce light loss, and further improve the performance of the battery.

[0027] In some embodiments, the ZnGa2O4-type material includes ZnGa2O4:Bi 3+ / Mn 4+ 、ZnGa2O4:Eu 3+ / Cr 3+ 、ZnGa2O4:Sb 3+ / Fe 3+ 、ZnGa2O4:Pr 3+ / V 5+ or one or more of them. In some embodiments, the ZnIn2O4-type material includes ZnIn2O4:Bi 3+ / Mn 4+ 、ZnIn2O4:Eu 3+ / Cr 3+ 、ZnIn2O4:Sb 3+ / Fe 3+ 、ZnIn2O4:Pr 3+ / V 5+ or one or more of them. In some embodiments, the ZnAl2O4-type material includes ZnAl2O4:Bi 3+ / Mn 4+ 、ZnAl2O4:Eu 3+ / Cr 3+ 、ZnAl2O4:Sb 3+ / Fe 3+ 、ZnAl2O4:Pr 3+ / V 5+ or one or more of them.

[0028] The above-mentioned spinel-type metal oxides all contain a sensitizer (Bi 3+ 、Eu 3+ 、Sb 3+ 、Pr 3+ ) and an activator (Mn 4+ 、Cr 3+ 、Fe 3+ 、V 5+), after the sensitizer absorbs light below 400 nm and transfers it to the activator, the conversion from ultraviolet to red light is realized, improving the thermal stability (>600 °C) and light conversion efficiency of the material. For example, ZnGa2O4:Bi 3+ / Mn 4+ In which Bi 3+ is usually used as a sensitizer and is the ultraviolet absorption center, and Mn 4+ acts as an activator to become the red light emission center, and the conversion from ultraviolet to red light is realized through the energy transfer of Bi 3+ →Mn 4+ .

[0029] In some embodiments, the refractive index of the conversion layer is 1.5 - 2.

[0030] In some embodiments, the thickness of the conversion layer is 50 nm - 100 nm.

[0031] In the embodiments of the present application, by controlling the refractive index n and thickness d of the conversion layer, when the phase change of the incident light (wavelength λ) traveling back and forth in the thin film is an odd multiple of π, destructive interference occurs, thereby achieving an antireflection effect. According to the thin film interference law: 2×(2π / λ)×n×d = (2m + 1)π (m = 0, 1, 2,...), after simplification, it is obtained: n×d = ((2m + 1)λ) / 4. By controlling the optical thickness n×d of the thin film, the antireflection can be achieved by using the interference effect. When the optical thickness is λ / 4, the reflected light is weakened due to destructive interference, thereby achieving the antireflection effect. For incident light in the wavelength range of λ from 400 nm to 740 nm, the refractive index of the conversion layer can be controlled to be 1.5 - 2 (for example, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0), and the thickness of the conversion layer is 50 nm - 100 nm (for example, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm). Different spinel-type metal oxide materials can form conversion layers with different refractive indices. For example, the conversion layer formed by ZnGa2O4:Bi 3+ / Mn 4+ has a refractive index n≈1.8.

[0032] In some embodiments, the conversion layer is formed by forming a conversion layer precursor solution; wherein, the conversion layer precursor solution includes a spinel-type metal oxide, an organic solvent, and a dispersant.

[0033] Organic solvents can dissolve spinel-type metal oxides, enabling them to be uniformly dispersed in the solution. They can also adjust physical properties such as the viscosity and surface tension of the solution, thereby optimizing the coating performance of the solution and improving the film-forming property and uniformity of the conversion layer. The dispersant can adsorb on the surface of spinel-type metal oxide particles, forming a protective film, increasing the electrostatic repulsion or steric hindrance between particles, and preventing particle aggregation. In addition, the dispersant can stably disperse solid particles, maintaining the uniformity of the solution even at high concentrations. The combined action of organic solvents and dispersants in the conversion layer precursor solution ensures the uniform dispersion and high-quality film formation of spinel-type metal oxides, thereby enhancing the performance of the conversion layer.

[0034] In an alternative embodiment, the mass ratio of the organic solvent to the spinel-type metal oxide is 8 - 12 (specifically, the mass ratio of the organic solvent to the spinel-type metal oxide is 8, 9, 10, 11, 12). In the conversion layer precursor solution, the mass percentage of the dispersant is 0.1wt% - 0.2wt%. Ultrasonically treating the conversion layer precursor solution containing spinel-type metal oxide, organic solvent, and dispersant for 30 - 40 minutes can fully mix the solution evenly.

[0035] In some embodiments, the organic solvent includes one or more of ethanol, propanol, and butanol. In some embodiments, the dispersant includes one or two of polyvinylpyrrolidone and ammonium citrate.

[0036] Ethanol, propanol, and butanol have good dissolution properties for spinel-type metal oxides. Polyvinylpyrrolidone and ammonium citrate can greatly improve the dispersion properties of spinel-type metal oxides in organic solvents.

[0037] In an alternative embodiment, the transparent conductive layer forms the bottom electrode, and the materials of the transparent conductive layer include, but are not limited to, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide, tungsten oxide, and fluorine-doped tin oxide (FTO). In some embodiments, magnetron sputtering can be used to deposit the transparent conductive oxide material on the surface of the transparent glass substrate to form the transparent conductive layer, and the thickness of the transparent conductive layer is 200nm - 800nm.

[0038] In an optional embodiment, the material of the hole transport layer includes but is not limited to one or more of [2-(9H-carbazol-9-yl)ethyl]phosphonic acid (2PACz), [2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl]phosphonic acid (MeO-2PACz), [4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid (Me-4PACz), [4-(9H-carbazol-9-yl)butyl]phosphonic acid (4PACz), poly(bis(4-phenyl)(2,4,6-trimethylphenyl)amine) (PTAA), triphenylamine derivatives, non-triphenylamine nitrogen-containing small molecule materials, cuprous iodide (CuI), cuprous thiocyanate (CuSCN), copper zinc tin sulfide (Cu2ZnSnS4), copper oxide (CuO), copper oxide (Cu2O), and nickel oxide (NiO2). In an optional embodiment, the hole transport layer material is first diluted in a diluent to form a hole transport material solution, and then the hole transport layer is prepared by spin coating, vacuum evaporation, magnetron sputtering, atomic layer deposition, or other methods, wherein the diluent includes one or both of ethanol and isopropanol. The thickness of the hole transport layer can be 1-100 nm.

[0039] In an optional embodiment, a perovskite material is dissolved in an organic solvent to form a perovskite precursor solution, and the perovskite precursor solution is applied to the surface of the hole transport layer by spin coating, slit coating, doctor blade coating, screen printing, inkjet printing, evaporation, spray coating, spray pyrolysis, or the like to obtain a perovskite light absorbing layer. The molar ratio of the perovskite material to the organic solvent is 0.001-1. The thickness of the perovskite light absorbing layer may be 10 nm-100 μm, or 300 nm-1200 nm; illustratively, the thickness of the perovskite light absorbing layer is 300 nm, 500 nm, 800 nm, 1000 nm, or 1200 nm. The band gap of the perovskite light absorbing layer may be 0.9-3.0 eV; illustratively, the band gap of the perovskite light absorbing layer is 0.9 eV, 1.68 eV, or 3.0 eV. Although the perovskite precursor solution includes an organic solvent, the organic solvent is removed during the process of forming the perovskite light-absorbing layer, and the finally formed perovskite light-absorbing layer includes the perovskite material but does not include the organic solvent.

[0040] In an optional embodiment, the perovskite light absorbing layer includes a perovskite material, and the perovskite material has an ABX3 structure; wherein A is a monovalent cation, including a mixture of one or more monovalent cations of cesium, rubidium, methylamine, and formamidinium; B is a divalent cation, including a mixture of one or more divalent cations of lead, copper, zinc, gallium, tin, and calcium; and X is a monovalent anion, including a mixture of one or more monovalent anions of iodine, bromine, chlorine, fluorine, and thiocyanate. For example, the perovskite material is Cs 0.25 FA 0.75 Pb(I0.8 Br 0.2 )3。

[0041] In alternative embodiments, the material of the electron transport layer includes, but is not limited to, one or more of TiO2, SnO2, ZnO, ZrO2, WO3, Zn2SnO4, gallium zinc oxide (GZO), indium zinc oxide (IZO), fluorine-doped tin oxide (FTO), indium tin oxide (ITO), BaSnO3, fullerenes, fullerene derivatives, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP). Exemplarily, the fullerenes can be selected from C 60 , C 70 one or two of them, and the fullerene derivatives can be selected from PCBM (such as [6,6]-phenyl-C61-butyric acid isomethyl ester, [6,6]-phenyl-C71-butyric acid isomethyl ester). Methods such as spin coating, slot coating, vacuum evaporation, thermal evaporation, magnetron sputtering, atomic layer deposition, spraying, spray pyrolysis, etc. can be used to prepare the electron transport layer. The thickness of the electron transport layer can be 10 nm - 100 nm.

[0042] In alternative embodiments, the top electrode includes, but is not limited to, one or more of Au, Ag, Al, Cu, transparent conductive oxide (TCO), graphene, nanocrystalline silicon. Methods such as thermal evaporation, vacuum evaporation, sputtering, atomic layer deposition, 3D printing, screen printing, inkjet printing, etc. can be used to prepare the electrode. The thickness of the top electrode can be 60 - 100 nm.

[0043] In alternative embodiments, a laser scribing process is used to form multiple perovskite sub-cells from a whole perovskite solar cell.

[0044] An embodiment of the present application provides a method for preparing a perovskite solar cell, including: S100: Provide a transparent glass substrate; S200: Sequentially form a transparent conductive layer, a hole transport layer, a perovskite absorption layer, an electron transport layer, and a top electrode on the transparent glass substrate; S300: Form a conversion layer on the side of the transparent glass substrate away from the transparent conductive layer; the material of the conversion layer includes spinel-type metal oxides.

[0045] In some embodiments, step S300, forming a conversion layer on the side of the transparent glass substrate away from the transparent conductive layer, includes: S301: Prepare a conversion layer precursor solution; wherein, the conversion layer precursor solution includes a spinel-type metal oxide, an organic solvent, and a dispersant; S302: Coat the conversion layer precursor solution on the side of the transparent glass substrate away from the transparent conductive layer, and after annealing treatment, form the conversion layer.

[0046] In the embodiments of the present application, during the annealing process, the organic solvent and the dispersant are removed, and the conversion layer only includes the spinel-type metal oxide, and other residual components can be ignored. Among them, the temperature of the annealing process is 120°C - 150°C (for example, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C).

[0047] The embodiments of the present application provide a preparation method for a spinel-type metal oxide for a perovskite solar cell, including: Mixing and grinding the raw materials of the spinel-type metal oxide to obtain a mixed powder; Performing a first sintering on the mixed powder in air, wherein the temperature of the first sintering is 350°C - 450°C; Performing a second sintering on the powder after the first sintering, wherein the temperature of the second sintering is 1200°C - 1300°C; Washing the powder after the second sintering with an acid solution to obtain an acid-washed product; Forming a spinel-type metal oxide from the acid-washed product by the sol-gel method.

[0048] In some embodiments, the raw materials of the spinel-type metal oxide include: ZnO, metal oxide M2O3, a first metal salt, and a second metal salt; Among them, M in the metal oxide is selected from one of Ga, In, and Al, the metal in the first metal salt is selected from one of Bi, Eu, Sb, and Pr, and the metal in the second metal salt is selected from one of Mn, Cr, Fe, and V.

[0049] In some embodiments, the spinel-type metal oxide includes one or more of ZnGa2O4-type materials, ZnIn2O4-type materials, and ZnAl2O4-type materials.

[0050] In some embodiments, the preparation method of the spinel-type metal oxide includes: grinding ZnO, metal oxide M2O3, a first metal salt, and a second metal salt into a mixed powder, first performing a first sintering on the mixed powder in air, then performing a second sintering, and finally washing with an acid solution and forming a spinel-type metal oxide by the sol-gel method. Among them, the spinel-type metal oxide formed by the sol-gel method is nanoparticles.

[0051] In some embodiments, the metal oxide M2O3 is selected from one of Ga2O3, In2O3, and Al2O3. In some embodiments, the first metal salt is selected from one of bismuth hydrate, europium hydrate, antimony hydrate, and praseodymium hydrate, specifically selected from one of Bi(NO3)3·5H2O, BiCl3·9H2O, Eu(NO3)3·6H2O, EuCl3·9H2O, Sb(NO3)3·5H2O, SbCl3·5H2O, Pr(NO3)3·6H2O, and PrCl3·9H2O. In some embodiments, the second metal salt is selected from one of manganese salts, chromium salts, iron salts, and vanadium salts, specifically selected from one of KMnO4, K2Cr2O7, Fe2(SO4)3, and V2(SO4)3.

[0052] The molar ratio of ZnO, metal oxide M2O3, the first metal salt, and the second metal salt is 1:(0.95 - 1.05):0.02:0.05 (for example, 1:0.95:0.02:0.05, 1:1:0.02:0.05, 1:1.05:0.02:0.05). The raw materials are ground by wet ball milling, and the grinding time is 3 - 5 hours (for example, 3 hours, 4 hours, 5 hours). The temperature of the first sintering is 350°C - 450°C (for example, 350°C, 400°C, 450°C), and the time of the first sintering is 1 hour - 3 hours (for example, 1 hour, 2 hours, 3 hours). The first sintering can remove organic substances and moisture. The temperature of the second sintering is 1200°C - 1300°C (for example, 1200°C, 1250°C, 1300°C), and the time of the second sintering is 6 hours - 8 hours (for example, 6 hours, 7 hours, 8 hours). A reducing gas of 5% H2 / 95% N2 is introduced during the second sintering process. The reducing gas causes the second metal salt (for example, KMnO4) to decompose into metal ions (for example, Mn 4+ ), which are incorporated into the lattice, while suppressing the volatilization of metal ions (for example, Bi 3+ ) in the first metal salt. After the second sintering, it is cooled to room temperature, and the residue of the unreacted second metal salt (for example, KMnO4) is removed by washing with dilute hydrochloric acid. [[ID=,8]]

[0053] In a specific embodiment, the preparation method of ZnGa2O4:Bi 3+ / Mn 4+ includes: grinding ZnO, Ga2O3, Bi(NO3)3·5H2O, and KMnO4 into a mixed powder, first pre-sintering the mixed powder in air for the first sintering, then performing the second sintering, and finally washing with an acid solution to form ZnGa2O4:Bi 3+ / Mn 4+ nanoparticles.

[0054] The following specific embodiments further illustrate the present application in detail, but should not be construed as a limitation to the present application. Without departing from the spirit and essence of the present application, any modification or replacement made to the methods, steps or conditions of the present application shall fall within the scope of the present application.

[0055] Example 1 As Figure 1 shown, the perovskite solar cell of Example 1 includes: A conversion layer 1, a transparent glass substrate 2, a transparent conductive layer 3, a hole transport layer 4, a perovskite absorption layer 5, an electron transport layer 6, and a top electrode 7, which are sequentially stacked; Among them, the material of the conversion layer 1 includes a spinel-type metal oxide.

[0056] The preparation method of the perovskite solar cell of Example 1 includes: S100a: Provide a transparent glass substrate; S200a: Sequentially form a transparent conductive layer, a hole transport layer, a perovskite absorption layer, an electron transport layer, and a top electrode on the transparent glass substrate; S301a: Prepare a conversion layer precursor solution, which includes a spinel-type metal oxide, an organic solvent, and a dispersant; among them, the spinel-type metal oxide is ZnGa2O4:Bi 3+ / Mn 4+ , the organic solvent is ethanol, the dispersant is polyvinylpyrrolidone and ammonium citrate, and the mass ratio C1 of the organic solvent to the spinel-type metal oxide is 10; S302a: Coat the conversion layer precursor solution on the side of the transparent glass substrate away from the transparent conductive layer, and anneal the organic solvent and the dispersant to form a conversion layer, the material of which includes a spinel-type metal oxide.

[0057] Examples 2 - 10 The specific structures and preparation methods of the perovskite solar cells of Examples 2 - 10 are basically the same as those of Example 1, except that the spinel-type metal oxides, organic solvents, dispersants, and the mass ratio C1 of the organic solvent to the spinel-type metal oxide in Examples 2 - 10 are different. The spinel-type metal oxides, organic solvents, dispersants, and the mass ratio C1 of the organic solvent to the spinel-type metal oxide in Examples 2 - 10 are shown in Table 1.

[0058] Table 1

[0059] To more clearly illustrate the technical effects of the embodiments of the present application, the structures and preparation methods of the perovskite solar cells of Comparative Example 1 are also pointed out.

[0060] Comparative Example 1 The specific structure and preparation method of the perovskite solar cell of Comparative Example 1 are basically the same as those of Example 1, except that the perovskite solar cell of Comparative Example 1 does not have a conversion layer, and the preparation method of the perovskite solar cell of Comparative Example 1 does not have steps S301a and S302a.

[0061] Next, performance tests were carried out on the perovskite solar cells provided in Examples 1-10 and Comparative Example 1 of the present application, so as to obtain the open-circuit voltage Voc, short-circuit current density Jsc, fill factor FF, photoelectric conversion efficiency PCE, transmittance and attenuation rate of the corresponding battery devices. The test results are shown in Table 2. Among them, the transmittance refers to the average transmittance of the perovskite solar cell in the wavelength range of 750nm - 1200nm. The attenuation rate refers to the percentage of the attenuation of the photoelectric conversion efficiency after the perovskite solar cell is subjected to an aging test under the condition of UV15 (ultraviolet 15 Kw.h).

[0062] Table 2 Performance test results of the perovskite solar cells of Examples 1-10 and Comparative Example 1

[0063] According to the data in Table 2, compared with Comparative Example 1, the perovskite solar cells of Examples 1-10 of the present application are provided with a conversion layer formed by a spinel-type metal oxide on the light incident surface of the transparent glass substrate. The open-circuit voltage, short-circuit current density, fill factor FF, photoelectric conversion efficiency and transmittance of the perovskite solar cells of Examples 1-10 are all significantly improved, and the attenuation rate is significantly reduced.

[0064] In summary, the perovskite solar cell of the embodiment of the present application is provided with a conversion layer formed by a spinel-type metal oxide on the light incident surface of the transparent glass substrate. The spinel-type metal oxide includes a sensitizer and an activator. The conversion layer can transfer short-wavelength light to the activator through the sensitizer and convert it into light within the perovskite light absorption range, thereby improving the photoelectric conversion efficiency of the perovskite battery, achieving an antireflection effect, and enhancing the ultraviolet stability of the perovskite solar cell.

[0065] The embodiment of the present application provides a photovoltaic module (not shown), including the perovskite solar cell of any of the above embodiments. The advantages possessed by the above perovskite solar cell are also possessed by this photovoltaic module, and will not be elaborated here.

[0066] Embodiments of the present application may provide a photovoltaic system, including the photovoltaic modules in the above embodiments. The advantages of the above photovoltaic modules are also possessed by the photovoltaic system, which will not be elaborated here. The application fields of the above photovoltaic system are extensive, not limited to photovoltaic power stations, such as ground power stations, rooftop power stations, and water surface power stations, but also include various devices and apparatuses that utilize solar energy for power generation, such as user solar power supplies, solar street lamps, solar cars, and solar buildings, etc. Of course, it can be understood that the application scenarios of the photovoltaic system are not limited thereto, that is to say, the photovoltaic system can be applied in all fields that require solar power generation. Taking the photovoltaic power generation system network as an example, the photovoltaic system may include a photovoltaic array, a busbar box, and an inverter. The photovoltaic array can be an array combination of multiple photovoltaic modules. For example, multiple photovoltaic modules can form multiple photovoltaic arrays. The photovoltaic array is connected to the busbar box, and the busbar box can collect the current generated by the photovoltaic array. The collected current flows through the inverter and is converted into alternating current required by the commercial power grid and then connected to the commercial power grid to achieve solar power supply.

[0067] It should be noted that the terms "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. are only for the convenience of describing the present application and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation. Therefore, it should not be construed as a limitation to the present application. The orientation terms "inner" and "outer" refer to the inside and outside relative to the contour of each component itself. For example, if the device in the drawing is inverted, the device described as "above other devices or structures" or "on top of other devices or structures" will be positioned as "below other devices or structures" or "beneath other devices or structures" afterwards. Thus, the exemplary term "above..." can include both the orientation of "above..." and "below...". The device can also be positioned in other different ways (rotated 90 degrees or in other orientations), and corresponding explanations are made for the relative spatial descriptions used here.

[0068] It should be noted that the terms "first", "second", etc. in the specification and claims of the present application and the above drawings are used to distinguish similar objects, and do not necessarily need to describe a specific order or sequence. It should be understood that such terms can be interchanged under appropriate circumstances, so that the embodiments of the present application described here can be implemented in an order other than those illustrated or described here. In addition, the terms "include" and "have" and any variations thereof are intended to cover non-exclusive inclusion. For example, a process, method, system, product, or device that includes a series of steps or units does not necessarily have to be limited to those steps or units clearly listed, but may include other steps or units that are not clearly listed or are inherent to these processes, methods, products, or devices.

[0069] It should also be noted that the "one embodiment", "another embodiment", "embodiment", etc. mentioned in this application refer to the specific features, structures or characteristics described in connection with that embodiment being included in at least one embodiment described in the general description of this application. The same expression appearing in multiple places in the specification does not necessarily refer to the same embodiment. Further, when describing a specific feature, structure or characteristic in connection with any one embodiment, it is intended that the implementation of such feature, structure or characteristic in combination with other embodiments also falls within the scope of this application.

[0070] In the above embodiments, the descriptions of the respective embodiments have their own emphases. For parts not detailed in a certain embodiment, reference may be made to the relevant descriptions of other embodiments.

[0071] It should also be noted that the above are only the preferred embodiments of this application, and do not limit the scope of patent protection of this application. Any equivalent structural or equivalent process transformation made using the content of the specification and drawings of this application, or directly or indirectly applied in other related technical fields, are similarly included in the scope of patent protection of this application.

Claims

1. A perovskite solar cell, characterized in that, Comprising: A conversion layer, a transparent glass substrate, a transparent conductive layer, a hole transport layer, a perovskite absorption layer, an electron transport layer, and a top electrode that are sequentially stacked; Wherein, the material of the conversion layer includes a spinel-type metal oxide.

2. The perovskite solar cell according to claim 1, wherein The spinel-type metal oxide includes one or more of a ZnGa2O4-type material, a ZnIn2O4-type material, and a ZnAl2O4-type material.

3. The perovskite solar cell according to claim 2, wherein The ZnGa2O4-based material includes ZnGa2O4:Bi 3+ / Mn 4+ 、ZnGa2O4:Eu 3+ / Cr 3+ 、ZnGa2O4:Sb 3+ / Fe 3+ 、ZnGa2O4:Pr 3+ / V 5+ or one or more of the above.

4. The perovskite solar cell according to claim 2, characterized in that, The ZnIn2O4-based material includes ZnIn2O4:Bi 3+ / Mn 4+ 、ZnIn2O4:Eu 3+ / Cr 3+ 、ZnIn2O4:Sb 3+ / Fe 3+ 、ZnIn2O4:Pr 3+ / V 5+ or one or more of the following 5. The perovskite solar cell according to claim 2, wherein, The ZnAl2O4-type material includes ZnAl2O4:Bi 3+ / Mn 4+ 、ZnAl2O4:Eu 3+ / Cr 3+ 、ZnAl2O4:Sb 3+ / Fe 3+ 、ZnAl2O4:Pr 3+ / V 5+ or one or more of the following 6. The perovskite solar cell according to claim 1, characterized in that, The refractive index of the conversion layer is 1.5 - 2.

7. The perovskite solar cell according to claim 1, characterized in that, The thickness of the conversion layer is 50 nm - 100 nm.

8. A preparation method of a spinel-type metal oxide for a perovskite solar cell, characterized in that, Comprising: Mixing and grinding the raw materials of the spinel-type metal oxide to obtain a mixed powder; Performing a first sintering on the mixed powder in air, wherein the temperature of the first sintering is 350°C - 450°C; Performing a second sintering on the powder after the first sintering, wherein the temperature of the second sintering is 1200°C - 1300°C; Washing the powder after the second sintering with an acid solution to obtain a pickling product; Forming the spinel-type metal oxide from the pickling product by a sol-gel method.

9. The preparation method of the spinel-type metal oxide according to claim 8, characterized in that, The raw materials of the spinel-type metal oxide include: ZnO, a metal oxide M2O3, a first metal salt, and a second metal salt; Wherein, M in the metal oxide is selected from one of Ga, In, and Al, the metal in the first metal salt is selected from one of Bi, Eu, Sb, and Pr, and the metal in the second metal salt is selected from one of Mn, Cr, Fe, and V.

10. A method for preparing a perovskite solar cell, characterized in that, Comprising: Providing a transparent glass substrate; Sequentially forming a transparent conductive layer, a hole transport layer, a perovskite absorption layer, an electron transport layer, and a top electrode on the transparent glass substrate; Forming a conversion layer on one side of the transparent glass substrate away from the transparent conductive layer; the material of the conversion layer includes a spinel-type metal oxide.

11. The preparation method of the perovskite solar cell according to claim 10, characterized in that, Forming a conversion layer on one side of the transparent glass substrate away from the transparent conductive layer, comprising: Preparing a conversion layer precursor solution; wherein, the conversion layer precursor solution includes the spinel-type metal oxide, an organic solvent, and a dispersant; Coating the conversion layer precursor solution on one side of the transparent glass substrate away from the transparent conductive layer, and performing annealing treatment to form a conversion layer.

12. The method for preparing a perovskite solar cell according to claim 11, wherein, The organic solvent includes one or more of ethanol, propanol, and butanol; and / or The dispersant includes one or two of polyvinylpyrrolidone and ammonium citrate.

13. A photovoltaic module, characterized in that, Comprising the perovskite solar cell according to any one of claims 1 to 7.

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