An anti-radiation perovskite solar cell and space photovoltaic cell

Abstract

The application discloses an anti-radiation perovskite solar cell and a space photovoltaic cell, and relates to the technical field of space photovoltaic cells. The anti-radiation perovskite solar cell comprises a perovskite layer, a methylamine halide layer and an anti-radical layer, the methylamine halide layer is arranged on the surface of the perovskite layer, the anti-radical layer is arranged on the surface of the methylamine halide layer, and the anti-radical layer is an oxide film layer containing metal elements with multiple valence states. The anti-radiation perovskite solar cell is prepared by introducing the additional methylamine halide layer and the anti-radical layer, the anti-gamma ray capability of the prepared perovskite solar cell is improved, the photoelectric conversion efficiency of the cell is simultaneously improved, and the blank of related research means in the field is made up.

Description

Technical Field

[0001] This invention relates to the field of space photovoltaic cell technology, and more specifically, to a radiation-resistant perovskite solar cell and a space photovoltaic cell. Background Technology

[0002] Recently, with my country's increasing emphasis on satellite launches and space data centers, new requirements have been placed on space photovoltaics. Currently used gallium arsenide (GaAs) solar cells are extremely expensive, making it difficult to meet the needs of large-scale deployment. Perovskite solar cells, due to their high energy-to-weight ratio, excellent photoelectric conversion efficiency, solution-based fabrication, and low cost, have attracted widespread attention and are expected to replace GaAs as the next-generation space photovoltaic cell technology.

[0003] However, the practical application of perovskite solar cells in space is limited by their stability. High-energy particles and cosmic rays (such as gamma rays) in space can damage perovskite thin films and solar cell devices. In particular, gamma rays can penetrate the radiation-resistant glass or other protective layers on top of the cell and directly irradiate the perovskite surface, thereby damaging the perovskite thin film and reducing the device's photoelectric conversion efficiency and cell stability.

[0004] In view of this, the present invention is proposed. Summary of the Invention

[0005] The purpose of this invention is to provide a radiation-resistant perovskite solar cell and a space photovoltaic cell. By introducing an additional halide methylamine layer and an anti-free base layer, this invention improves the gamma-ray resistance of the prepared perovskite solar cell and simultaneously improves the photoelectric conversion efficiency of the cell, thereby filling the gap in related research methods in the field.

[0006] This invention is implemented as follows: In a first aspect, the present invention provides a radiation-resistant perovskite solar cell, comprising a perovskite layer, a methylamine halide layer, and an anti-free radical layer, wherein the methylamine halide layer is disposed on the surface of the perovskite layer, and the anti-free radical layer is disposed on the surface of the methylamine halide layer, wherein the anti-free radical layer is an oxide film layer containing a multivalent metal element.

[0007] In an optional embodiment, the metallic element includes at least one selected from europium, iron, copper, manganese, chromium, vanadium, and lead.

[0008] In an optional embodiment, the anti-free layer is at least one of europium trioxide and iron oxide, and when the anti-free layer is a mixture of europium trioxide and iron oxide, the mass ratio of europium trioxide to iron oxide is (1-10):(1-10).

[0009] In an optional embodiment, the anti-free base layer is a mixture of europium trioxide and iron oxide deposited.

[0010] In an optional embodiment, the anti-free base layer is formed by first depositing europium trioxide and then depositing iron oxide.

[0011] In an optional embodiment, the halogen element in the halomethylamine layer includes at least one of iodine, bromine, and chlorine.

[0012] In an optional embodiment, the methyl halide layer is formed by coating the perovskite layer with a methyl halide solution, wherein the concentration of methyl halide in the methyl halide solution is 0.01-10 mol / L.

[0013] In an optional embodiment, the thickness of the methyl halide layer is 0.1-50 nm, and the thickness of the anti-free radical layer is 0.1-50 nm; And / or, the thickness ratio of the halomethylamine layer to the antifreeze base layer is (1-2):(1-2).

[0014] In an optional embodiment, the radiation-resistant perovskite solar cell further includes a first carrier transport layer, a second carrier transport layer, a conductive electrode, and a transparent electrode. The first carrier transport layer is disposed on the lower surface of the perovskite layer, the conductive electrode is disposed on the lower surface of the first carrier transport layer, the second carrier transport layer is disposed on the upper surface of the anti-free base layer, and the transparent electrode is disposed on the upper surface of the second carrier transport layer.

[0015] In a second aspect, the present invention provides a space photovoltaic cell, which includes a radiation-resistant perovskite solar cell as described in any of the above embodiments.

[0016] The present invention has the following beneficial effects: This invention provides a radiation-resistant perovskite solar cell by sequentially introducing a methylamine halide layer and an anti-free radical layer on the surface of a perovskite layer. Under gamma irradiation, the chemical bonds in the methylamine halide layer (MAPbX3, where X = one or more of I, Br, and Cl) break, generating free radicals such as CH3, X, and NH3X. After gamma irradiation ceases, these free radicals combine with defects at the top of the bottom perovskite layer. However, Pb inevitably appears in this methylamine halide layer during irradiation. 0 In addition to defects such as free radicals being highly reactive and easily volatilized and lost, this invention addresses these issues by introducing an anti-free radical layer, which utilizes different valence metal elements to control the Pb generated in the bottom perovskite film. 0Defects are treated with oxidation to reduce their number; the anti-free radical layer, composed of a dense oxide film, effectively blocks the escape of free radicals generated during irradiation. Simultaneously introducing a methylamine halide layer and an anti-free radical layer significantly reduces defects caused by gamma ray irradiation, enhances the self-healing performance of the perovskite layer under gamma ray irradiation, thereby greatly improving the cosmic ray resistance stability of perovskite solar cells and simultaneously increasing the photoelectric conversion efficiency of the cells. Attached Figure Description

[0017] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0018] Figure 1 This is a schematic diagram of the structure of the radiation-resistant perovskite solar cell provided by the present invention; Figure 2 Current density-voltage test curves of perovskite solar cells of different examples before irradiation were plotted for experimental examples of the present invention. Figure 3 The current density-voltage test curves of different examples of perovskite solar cells after irradiation are plotted for experimental examples of the present invention.

[0019] Icons: 100 - Radiation-resistant perovskite solar cell; 101 - Conductive electrode; 102 - First carrier transport layer; 103 - Perovskite layer; 104 - Methylamine halide layer; 105 - Anti-free base layer; 106 - Second carrier transport layer; 107 - Transparent electrode. Detailed Implementation

[0020] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0021] Please see Figure 1 The present invention provides a radiation-resistant perovskite solar cell 100, which includes a perovskite layer 103, a methylamine halide layer 104, and an anti-free radical layer 105. The methylamine halide layer 104 is disposed on the surface of the perovskite layer 103, and the anti-free radical layer 105 is disposed on the surface of the methylamine halide layer 104. The anti-free radical layer 105 is an oxide film layer containing multivalent metal elements.

[0022] This invention introduces a methylamine halide layer 104 and an anti-free radical layer 105 sequentially onto the surface of a perovskite layer 103. Under gamma irradiation, the chemical bonds in the methylamine halide layer 104 (MAPbX3, where X = one or more of I, Br, and Cl) break, generating free radicals such as CH3, X, and NH3X. After gamma irradiation ceases, these free radicals bind to defects at the top of the bottom perovskite layer 103. However, Pb inevitably appears in the methylamine halide layer 104 during irradiation. 0 In addition to defects such as free radicals being highly reactive and easily volatilized and lost, this invention addresses these issues by introducing an anti-free radical layer 105, which utilizes different valence metal elements to control the Pb generated in the bottom perovskite film. 0 Defects are treated with oxidation to reduce their number; the anti-free radical layer 105, composed of a dense oxide film, effectively blocks the escape of free radicals generated during irradiation. By simultaneously introducing the methylamine halide layer 104 and the anti-free radical layer 105, defects caused by gamma ray irradiation can be significantly reduced, and the self-healing performance of the perovskite layer 103 under gamma ray irradiation can be improved, thereby greatly improving the stability of the perovskite solar cell against cosmic rays and simultaneously increasing the photoelectric conversion efficiency of the cell.

[0023] Specifically, the methyl halide layer 104 is formed by coating a methyl halide solution onto the perovskite layer 103, wherein the concentration of methyl halide in the solution is 0.01-10 mol / L. Various coating methods exist, and no specific limitation is made in this invention.

[0024] The anti-free base layer 105 is formed by directly depositing metal oxides onto the surface of the methyl halide layer 104. Commonly used methods include chemical vapor deposition (CVD), physical vapor deposition (PVD), electrodeposition, or atomic layer deposition (ALD). This invention does not limit the specific operation, as long as it can achieve the deposition of metal oxides onto the surface of the methyl halide layer 104.

[0025] The metallic element includes at least one of europium, iron, copper, manganese, chromium, vanadium, and lead. Europium, iron, copper, manganese, chromium, vanadium, and lead are all metallic elements with different valence states. In this invention, high-valence oxides of the aforementioned europium, iron, copper, manganese, chromium, vanadium, and lead are preferably used as the anti-free radical layer 105.

[0026] Preferably, the metallic elements are europium and iron, wherein the oxides of europium include europium trioxide (europium has a valence state of +3) and europium oxide (europium has a valence state of +2), and the oxides of iron include iron oxide (iron has a valence state of +3), ferrous oxide (iron has a valence state of +2), and iron(II,III) oxide (iron has valence states of +2 and +3).

[0027] In this invention, the anti-free layer 105 is at least one of europium trioxide and iron oxide. When the anti-free layer 105 is a mixture of europium trioxide and iron oxide, the mass ratio of europium trioxide to iron oxide is (1-10):(1-10). In this invention, the oxidation of Pb can be improved by compounding europium trioxide and iron oxide. 0 The defects are reduced to europium oxide, ferrous oxide or iron oxide in a low valence state. The combination of the two can make the free radical scavenging layer 105 more compact and the free radical scavenging effect better, thus synergistically improving the anti-radiation effect.

[0028] Furthermore, the present invention also defines the thickness of the introduced methyl halide layer 104 and the anti-freezing layer 105, wherein the thickness of the methyl halide layer 104 is 0.1-50 nm, and the thickness of the anti-freezing layer 105 is 0.1-50 nm. By defining these thicknesses, enhanced perovskite gamma-ray stability can be achieved, while simultaneously improving battery efficiency. Preferably, the thickness ratio of the methyl halide layer to the anti-freezing layer is (1-2):(1-2).

[0029] The radiation-resistant perovskite solar cell 100 also includes a first carrier transport layer 102, a second carrier transport layer 106, a conductive electrode 101, and a transparent electrode 107. The first carrier transport layer 102 is disposed on the lower surface of the perovskite layer 103, the conductive electrode 101 is disposed on the lower surface of the first carrier transport layer 102, the second carrier transport layer 106 is disposed on the upper surface of the anti-free base layer 105, and the transparent electrode 107 is disposed on the upper surface of the second carrier transport layer 106.

[0030] The perovskite layer 103 is composed of ABX3, where A represents monovalent cations such as formamidinium (FA), methylamine (MA), Cs, and Rb; B represents divalent metal cations such as Pb and Sn; and X represents halogens such as I, Br, and Cl. The A, B, and X-position ions in the perovskite used in this method are one or more of those shown above, and the X-position must contain I ions, with no specific ratio limit. Methods for preparing the perovskite layer 103 include, but are not limited to, spin coating, blade coating, slot coating, vacuum evaporation, and roll-to-roll deposition. The perovskite solution used is FA, a commonly used material in the perovskite photovoltaic field. x Cs 1-x Pb(I y Br 1-y )3, where x = 0.01-0.99, y = 0.01-0.99. Any commercially available perovskite solution can be used as the coating material for the perovskite layer in this application, and no specific limitations are imposed on it in this application.

[0031] The first carrier transport layer 102 and the second carrier transport layer 106 have different polarities, being P / N type. The P-type material is a combination of one or more commonly used hole transport molecules such as PTAA, self-assembled single molecules (SAM), nickel oxide, etc., while the N-type material is a combination of one or more commonly used electron transport molecules such as C60, PCBM, SnO2, etc.

[0032] The selection of transparent electrode 107 and conductive electrode 101 can also refer to conventional perovskite solar cells, and no specific limitation is made in this invention.

[0033] The gamma rays are irradiated from the top of the perovskite, ultimately achieving a complete solar cell structure.

[0034] The method for preparing the radiation-resistant perovskite solar cell 100 provided by the present invention is simple and can be carried out in accordance with the conventional method for preparing perovskite solar cells. No specific limitations are imposed in the present invention.

[0035] In addition, the present invention provides a space photovoltaic cell, which includes the above-mentioned radiation-resistant perovskite solar cell 100.

[0036] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0037] Example 1 This embodiment provides a radiation-resistant perovskite solar cell 100, which includes, from bottom to top: a conductive electrode 101, a first carrier transport layer 102, a perovskite layer 103, a methylamine halide layer 104, an anti-free radical layer 105, a second carrier transport layer 106, and a transparent electrode 107.

[0038] The preparation method includes: using indium tin oxide (ITO) as a conductive electrode 101; depositing nickel oxide on the conductive electrode 101 as a first carrier transport layer 102 (hole transport layer); and then spin-coating a perovskite solution (FA). 0.83 Cs 0.17 Pb(I 0.8 Br 0.2 3) A perovskite layer 103 was prepared; methyl iodide with a concentration of 1 mol / L was coated on the surface of the perovskite layer 103 to prepare a methyl iodide halide layer 104 with a thickness of 10 nm; subsequently, a mixture of europium trioxide and iron oxide was deposited on the surface of the methyl iodide halide layer 104 by physical vapor deposition to obtain a free radical scavenging layer 105 with a thickness of 10 nm; then C was deposited separately. 60 Tin oxide (SnO2) is used as the second carrier transport layer 106 (electron transport layer), and ITO is deposited as the transparent electrode 107.

[0039] Example 2 This embodiment is basically the same as Embodiment 1, except that in this comparative example, the halomethylamine layer 104 is a brominated methylamine layer with a thickness of 20 nm, and the thickness of the anti-free base layer 105 is 10 nm.

[0040] Example 3 This embodiment is basically the same as Embodiment 1, except that in this comparative example, the halomethylamine layer 104 is a methylamine chloride layer with a thickness of 10 nm, and the thickness of the anti-free base layer 105 is 20 nm.

[0041] Example 4 This embodiment is basically the same as Embodiment 1, except that in this embodiment, the anti-free base layer 105 is first deposited with europium trioxide and then with iron oxide, and the ratio of europium trioxide to iron oxide is 1:1.

[0042] Example 5 This embodiment is basically the same as Embodiment 1, except that the anti-free base layer 105 in this embodiment uses only iron oxide.

[0043] Example 6 This embodiment is basically the same as Embodiment 1, except that the anti-free base layer 105 in this embodiment uses only europium oxide.

[0044] Example 7 This embodiment is basically the same as Embodiment 1, except that the thickness of both the halomethylamine layer 104 and the anti-free base layer 105 in this embodiment is 25 nm.

[0045] Comparative Example 1 This comparative example is basically the same as Example 1, except that the halide methylamine layer 104 and the anti-free base layer 105 are not introduced in this comparative example. The structure of the perovskite solar cell in this comparative example includes, from bottom to top: a conductive electrode 101, a first carrier transport layer 102, a perovskite layer 103, a second carrier transport layer 106, and a transparent electrode 107.

[0046] Comparative Example 2 This comparative example is basically the same as Example 1, except that the anti-free base layer 105 is not introduced in this comparative example. The structure of the perovskite solar cell in this comparative example includes, from bottom to top: a conductive electrode 101, a first carrier transport layer 102, a perovskite layer 103, a methylamine halide layer 104, a second carrier transport layer 106, and a transparent electrode 107.

[0047] Comparative Example 3 This comparative example is basically the same as Example 1, except that the halide methylamine layer 104 is not introduced in this comparative example. The structure of the perovskite solar cell in this comparative example includes, from bottom to top: a conductive electrode 101, a first carrier transport layer 102, a perovskite layer 103, an anti-free base layer 105, a second carrier transport layer 106, and a transparent electrode 107.

[0048] Comparative Example 4 This comparative example is basically the same as Example 1, except that in this comparative example, methyl halogenated amine is not introduced as a layer, but is directly added to the perovskite precursor solution to prepare a perovskite containing methyl halogenated amine. The amount added is consistent with the amount of methyl halogenated amine layer 104 used in Example 1. The structure of the perovskite solar cell in this comparative example, from bottom to top, includes: a conductive electrode 101, a first carrier transport layer 102, a perovskite layer containing methyl halogenated amine 103, an anti-free radical layer 105, a second carrier transport layer 106, and a transparent electrode 107.

[0049] Experimental Example 1 The perovskite solar cells prepared in Examples 1-7 and Comparative Examples 1-4 were subjected to photovoltaic performance testing. The testing method involved placing the perovskite solar cells under simulated solar spectrum (AM 1.5G), extracting voltage-current characteristic curves using a digital source meter, and calculating the fill factor and photoelectric conversion efficiency. Voltage-current test curves of the perovskite solar cells prepared in Examples 1-7 and Comparative Examples 1-4 were plotted; the results are shown in [link to relevant documentation]. Figure 2 and Figure 3 .

[0050] The test results are as follows: Table 1. Statistical table of photovoltaic performance test results for different examples

[0051] From Table 1, Figure 2 and Figure 3 It can be seen that Example 1 exhibits the highest efficiency before and after irradiation, reaching 25.17% and 24.28%, respectively; the methyl halide layer 104 and the anti-free radical layer 105 achieve the best results at specific thicknesses and ratios. Furthermore, Comparative Examples 1-3 show that the radiation resistance effect without the addition of the methyl halide layer and the anti-free radical layer is significantly worse than that of Example 1. Simultaneously, the radiation resistance effect of applying either the methyl halide layer or the anti-free radical layer alone is weaker than that of Example 1, demonstrating a synergistic effect between the methyl halide layer and the anti-free radical layer. Comparative Example 4 shows that when methyl halide is not introduced as a layer but directly added to the perovskite precursor solution to prepare perovskites containing methyl halide, its effect is still significantly lower than that of Example 1, proving that the method of setting the methyl halide is crucial.

[0052] In summary, this invention provides a radiation-resistant perovskite solar cell 100 by sequentially introducing a methylamine halide layer 104 and an anti-free radical layer 105 onto the surface of the perovskite layer 103. The methylamine halide layer 104 (MAPbX3, where X = one or more of I, Br, and Cl) undergoes chemical bond breakage under gamma irradiation, generating free radicals such as CH3, X, and NH3X. After gamma irradiation ceases, these free radicals combine with defects at the top of the bottom perovskite layer 103. However, Pb inevitably appears in the methylamine halide layer 104 during irradiation. 0 In addition to defects such as free radicals being highly reactive and easily volatilized and lost, this invention addresses these issues by introducing an anti-free radical layer 105, which utilizes different valence metal elements to control the Pb generated in the bottom perovskite film. 0 Defects are treated with oxidation to reduce their number; the anti-free radical layer 105, composed of a dense oxide film, effectively blocks the escape of free radicals generated during irradiation. By simultaneously introducing the methylamine halide layer 104 and the anti-free radical layer 105, defects caused by gamma ray irradiation can be significantly reduced, and the self-healing performance of the perovskite layer 103 under gamma ray irradiation can be improved, thereby greatly improving the stability of the perovskite solar cell against cosmic rays and simultaneously increasing the photoelectric conversion efficiency of the cell.

[0053] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A radiation-resistant perovskite solar cell, characterized in that, It includes a perovskite layer, a methylamine halide layer, and an anti-free radical layer. The methylamine halide layer is disposed on the surface of the perovskite layer, and the anti-free radical layer is disposed on the surface of the methylamine halide layer. The anti-free radical layer is an oxide film layer containing a multivalent metal element, and the anti-free radical layer is at least one of europium trioxide and iron oxide. The thickness of the methylamine halide layer is 0.1-50 nm, and the thickness of the anti-free radical layer is 0.1-50 nm. The thickness ratio of the methylamine halide layer to the anti-free radical layer is (1-2):(1-2).

2. The radiation-resistant perovskite solar cell according to claim 1, characterized in that, When the anti-free base layer is a mixture of europium trioxide and iron oxide, the mass ratio of europium trioxide to iron oxide is (1-10):(1-10).

3. The radiation-resistant perovskite solar cell according to claim 2, characterized in that, The anti-free base layer is a mixture of europium trioxide and iron oxide deposited.

4. The radiation-resistant perovskite solar cell according to claim 2, characterized in that, The anti-free base layer is formed by first depositing europium trioxide and then depositing iron oxide.

5. The radiation-resistant perovskite solar cell according to claim 1, characterized in that, The halogen element in the halomethylamine layer includes at least one of iodine, bromine, and chlorine.

6. The radiation-resistant perovskite solar cell according to claim 1, characterized in that, The methyl halide layer is formed by coating the perovskite layer with a methyl halide solution, wherein the concentration of methyl halide in the methyl halide solution is 0.01-10 mol / L.

7. The radiation-resistant perovskite solar cell according to claim 1, characterized in that, The radiation-resistant perovskite solar cell further includes a first carrier transport layer, a second carrier transport layer, a conductive electrode, and a transparent electrode. The first carrier transport layer is disposed on the lower surface of the perovskite layer, the conductive electrode is disposed on the lower surface of the first carrier transport layer, the second carrier transport layer is disposed on the upper surface of the anti-free base layer, and the transparent electrode is disposed on the upper surface of the second carrier transport layer.

8. A space photovoltaic cell, characterized in that, It includes the radiation-resistant perovskite solar cell as described in any one of claims 1-7.

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