A perovskite precursor solution, a perovskite solar cell, a photovoltaic energy storage system, a preparation method and applications

Abstract

This invention provides a perovskite precursor solution, a perovskite solar cell, a photovoltaic energy storage system, a preparation method, and applications, including Cs. 0.05 FA 0.95 PbI3 and 2-thiopheneformyl chloride. Based on the passivation modification of the perovskite layer by 2-thiopheneformyl chloride, with the increase of the number of perovskite solar cells and aqueous vanadium-based zinc-ion cells in the photovoltaic energy storage system, not only can the cell efficiency of the perovskite solar cells be further improved, but the charging efficiency of the perovskite solar cells for aqueous vanadium-based zinc-ion cells can also be improved, ultimately resulting in a significant increase in the total energy conversion efficiency of the photovoltaic energy storage system.

Description

Technical Field

[0001] This invention relates to the field of aqueous vanadium-based zinc-ion batteries, and in particular to a perovskite precursor solution, a perovskite solar cell, a photovoltaic energy storage system, a preparation method, and applications. Background Technology

[0002] With the rapid development of next-generation portable electronic devices, the demand for photovoltaic energy storage systems is gradually increasing. A photovoltaic energy storage system typically consists of two parts: photovoltaic cells and rechargeable batteries. Correspondingly, the overall efficiency of a photovoltaic energy storage system is determined by both the photoelectric conversion efficiency of the photovoltaic cells and the charging efficiency of the rechargeable batteries.

[0003] Among the many types of rechargeable batteries, aqueous rechargeable batteries have the advantages of high safety, low cost and easy processing. In particular, aqueous vanadium-zinc ion batteries have attracted widespread attention due to their advantages of high capacity, low redox potential and high stability. Therefore, most photovoltaic energy storage systems use aqueous vanadium-zinc ion batteries.

[0004] Among various photovoltaic cells, perovskite solar cells have high photoelectric conversion efficiency, so most photovoltaic energy storage systems have begun to use perovskite solar cells as the main photovoltaic cells.

[0005] To convert as much solar energy as possible into electrical energy and then store it in a photovoltaic (PV) energy storage system, such systems typically consist of multiple perovskite solar cells and multiple aqueous vanadium-zinc-ion batteries. However, actual testing has revealed that while the efficiency of the perovskite solar cells improves to some extent as the number of perovskite and aqueous vanadium-zinc-ion batteries in the PV energy storage system increases, the overall energy conversion efficiency of the PV energy storage system does not change significantly and sometimes even decreases. Summary of the Invention

[0006] Based on this, the present invention addresses the problem of low overall energy conversion efficiency of photovoltaic energy storage systems as the number of perovskite solar cells and aqueous vanadium-zinc ion batteries increases, and provides a perovskite precursor solution, a perovskite solar cell, a photovoltaic energy storage system, a preparation method, and applications.

[0007] The technical solution provided by this invention is as follows:

[0008] A perovskite precursor liquid comprising Cs 0.05 FA 0.95 PbI3 and 2-thiophenecarboxyl chloride.

[0009] In some embodiments of this application, Cs in the perovskite precursor solution 0.05 FA 0.95The ratio between the amount of PbI3 and the volume of 2-thiophenecarboxyl chloride is 1.6 × 10⁻⁶. -3 mol: 2μL.

[0010] A perovskite solar cell includes a conductive glass layer, a hole transport layer, a perovskite layer, an electron transport layer, and an electrode layer arranged in sequence, wherein the perovskite layer is obtained by spin-coating with a perovskite precursor solution.

[0011] A photovoltaic energy storage system includes a photovoltaic module and a charging module connected in series with the photovoltaic module. The charging module includes at least one aqueous vanadium-based zinc-ion battery, and the photovoltaic module includes at least two perovskite solar cells connected in series.

[0012] In some embodiments of this application, the method for preparing the positive electrode sheet in the aqueous vanadium-based zinc-ion battery includes:

[0013] 0.546 g of vanadium pentoxide, 4 mL of hydrogen peroxide, 0.3 mmol of strontium acetate, and 0.1 mL of 3,4-ethylenedioxythiophene were added to 70 mL of deionized water and then reacted in a reactor at 180 °C for 4 hours to obtain a positive electrode slurry.

[0014] The positive electrode slurry is coated onto the current collector, and then dried, rolled and punched to obtain the positive electrode sheet;

[0015] In the aforementioned aqueous vanadium-based zinc-ion battery, the negative electrode is zinc foil, the separator is a glass fiber membrane, the solute of the electrolyte is zinc trifluoromethanesulfonate, and the solvent of the electrolyte is water.

[0016] In some embodiments of this application, the method for fabricating the perovskite solar cell includes:

[0017] A 5 mg / mL nickel oxide aqueous solution was spin-coated onto a conductive glass layer and then dried at 150 °C to obtain the hole transport layer. The spin-coating speed of the nickel oxide aqueous solution was 4000 rpm and the spin-coating time was 30 s.

[0018] FAI, CsI, and PbI₂ were dissolved in a mixed solvent of DMF and DMSO at a molar ratio of 0.95:0.05:1 to form a 1.6 M CsI solution. 0.05 FA 0.95 A PbI3 solution in which the volume ratio of DMF to DMSO is 4:1;

[0019] Take 1 mL of Cs 0.05 FA 0.95 PbI3 solution and 2 μL of 2-thiophenecarboxyl chloride were mixed to obtain perovskite precursor solution;

[0020] The perovskite precursor solution is spin-coated onto the hole transport layer and then annealed at 150°C to obtain the perovskite layer; wherein the spin-coating speed of the perovskite precursor solution is 4000 rpm and the spin-coating time is 30 s, and chlorobenzene is added dropwise during the spin-coating process of the perovskite precursor solution.

[0021] A chlorobenzene solution of PCBM was spin-coated onto the perovskite layer to obtain an electron transport layer, wherein the concentration of PCBM was 30 mg / mL, the spin-coating speed of the chlorobenzene solution of PCBM was 3000 rpm, and the spin-coating time was 30 s.

[0022] A 100 nm thick layer of silver is deposited on the electron transport layer to obtain an electrode layer.

[0023] In some embodiments of this application, the number of perovskite solar cells is three, and the number of aqueous vanadium-based zinc-ion cells is two.

[0024] A method for fabricating a perovskite solar cell, comprising:

[0025] An aqueous solution of nickel oxide is spin-coated onto a conductive glass layer and then dried to obtain a hole transport layer.

[0026] The perovskite precursor liquid is spin-coated onto the hole transport layer and then annealed to obtain the perovskite layer.

[0027] A chlorobenzene solution of PCBM is spin-coated onto the perovskite layer to obtain an electron transport layer;

[0028] Silver is deposited on the electron transport layer to obtain the electrode layer.

[0029] In some embodiments of this application, the concentration of the nickel oxide aqueous solution is 5 mg / mL, the spin coating speed of the nickel oxide aqueous solution is 4000 rpm, the spin coating time is 30 s, and the drying temperature is 150°C.

[0030] The spin coating speed of the perovskite precursor solution is 4000 rpm and the spin coating time is 30 s. Chlorobenzene is added dropwise during the spin coating process of the perovskite precursor solution.

[0031] The concentration of the chlorobenzene solution in the PCBM is 30 mg / mL, the spin coating speed of the chlorobenzene solution in the PCBM is 3000 rpm, and the spin coating time is 30 s.

[0032] The thickness of the electrode layer is 100 nm;

[0033] The preparation method of the perovskite precursor solution includes: dissolving FAI, CsI, and PbI2 in a mixed solvent of DMF and DMSO at a molar ratio of 0.95:0.05:1 to form a CsI solution with a concentration of 1.6M.0.05 FA 0.95 A PbI3 solution in which the volume ratio of DMF to DMSO is 4:1;

[0034] Take 1 mL of Cs 0.05 FA 0.95 A PbI3 solution was mixed with 2 μL of 2-thiophenecarboxyl chloride to obtain a perovskite precursor solution.

[0035] Application of 2-thiophenecarboxyl chloride in improving the photoelectric conversion efficiency of perovskite solar cells and / or the total energy conversion efficiency of photovoltaic energy storage systems.

[0036] The beneficial effects of this invention are as follows:

[0037] Through Cs 0.05 FA 0.95 Adding 2-thiophenecarboxyl chloride to PbI3 can improve Cs 0.05 FA 0.95 Uncoordinated Pb in PbI3 2+ It interacts with the C=O in 2-thiopheneformyl chloride, while Cs 0.05 FA 0.95 Iodine defects in PbI3 can be passivated by chloride ions in 2-thiophenecarboxyl chloride. This not only improves the thin film quality of the perovskite layer in perovskite solar cells, but also suppresses charge accumulation at the interface between the perovskite layer and the electron transport layer, which is beneficial for electron transfer and thus helps to improve the photoelectric conversion efficiency of perovskite solar cells.

[0038] Based on the passivation modification of the perovskite layer by 2-thiophenecarboxyl chloride, with the increase in the number of perovskite solar cells and aqueous vanadium-based zinc-ion cells in the photovoltaic energy storage system, not only can the cell efficiency of the perovskite solar cells be further improved, but also the charging efficiency of the perovskite solar cells for the aqueous vanadium-based zinc-ion cells can be improved, ultimately resulting in a significant increase in the total energy conversion efficiency of the photovoltaic energy storage system. Attached Figure Description

[0039] Figure 1 XPS images (Pb 4f) of the perovskite layer in Comparative Example 1 and Example 1 of the present invention.

[0040] Figure 2 XPS images (I 3d) of the perovskite layer in Comparative Example 1 and Example 1 of the present invention.

[0041] Figure 3 The energy level diagrams are shown for the perovskite solar cells in Comparative Example 1 and Example 1 of this invention.

[0042] Figure 4The diagram shows the power analysis of the photovoltaic energy storage system in Comparative Example 1 and Example 1 of this invention.

[0043] Figure 5 The diagram shows the power analysis of the photovoltaic energy storage system in Embodiment 2 and Comparative Example 2 of the present invention.

[0044] Figure 6 This is a SEM image of the perovskite layer in Comparative Example 3 of the present invention;

[0045] Figure 7 This is a SEM image of the perovskite layer in Example 3 of the present invention;

[0046] Figure 8 This is a SEM image of the perovskite layer in Example 4 of the present invention;

[0047] Figure 9 This is a SEM image of the perovskite layer in Example 5 of the present invention. Detailed Implementation

[0048] To make the above-mentioned objects, features, and advantages of the present invention more apparent and understandable, specific embodiments of the present invention are described in detail below. Many specific details are set forth in the following description to provide a thorough understanding of the present invention. However, the present invention can be practiced in many other ways different from those described herein, and those skilled in the art can make similar modifications without departing from the spirit of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0049] In all subsequent embodiments and comparative examples of this application, the photovoltaic energy storage system includes a photovoltaic module and a charging module connected in series with the photovoltaic module. The charging module includes at least one aqueous vanadium-zinc-ion battery; when there are two or more aqueous vanadium-zinc-ion batteries, all of them are connected in series. The photovoltaic module includes at least two perovskite solar cells connected in series.

[0050] A perovskite solar cell comprises a conductive glass layer, a hole transport layer, a perovskite layer, an electron transport layer, and an electrode layer arranged in sequence.

[0051] The method for preparing the perovskite solar cell includes:

[0052] Step 101: Spin-coat a 5 mg / mL nickel oxide aqueous solution onto the conductive glass layer, and then dry it at 150°C for 30 min to obtain the hole transport layer. The spin-coating speed of the nickel oxide aqueous solution is 4000 rpm, and the spin-coating time is 30 s.

[0053] Step 102: Spin-coat the perovskite precursor solution onto the hole transport layer, and then anneal at 150°C for 30 min to obtain the perovskite layer. The spin-coating speed of the perovskite precursor solution is 4000 rpm, the spin-coating time is 30 s, and chlorobenzene is added dropwise as an anti-solvent during the spin-coating process.

[0054] Step 103: Spin-coat the perovskite layer with a chlorobenzene solution of PCBM to obtain an electron transport layer. The concentration of PCBM is 30 mg / mL, the spin-coating speed of the chlorobenzene solution is 3000 rpm, and the spin-coating time is 30 s.

[0055] Step 104: Deposit a 100 nm thick layer of silver onto the electron transport layer to obtain an electrode layer.

[0056] In all subsequent embodiments and comparative examples of this application, the structure of the aqueous vanadium-based zinc-ion battery is the same. The preparation method of the positive electrode in the aqueous vanadium-based zinc-ion battery includes: adding 0.546g of vanadium pentoxide, 4mL of hydrogen peroxide, 0.3mmol of strontium acetate, and 0.1mL of 3,4-ethylenedioxythiophene to 70mL of deionized water, and then reacting in a reactor at 180°C for 4 hours to obtain a positive electrode slurry; coating the positive electrode slurry onto a current collector, and then drying, rolling, and punching to obtain the positive electrode sheet. The negative electrode of the aqueous vanadium-based zinc-ion battery is zinc foil, the separator is a glass fiber membrane, the solute of the electrolyte is zinc trifluoromethanesulfonate, and the solvent of the electrolyte is water.

[0057] Comparative Example 1:

[0058] This comparative example provides a photovoltaic energy storage system, which specifically includes two perovskite solar cells and one aqueous vanadium-based zinc-ion battery.

[0059] In this comparative example, the perovskite precursor solution was prepared by dissolving FAI (formamidinium iodide), CsI, and PbI2 in a mixed solvent of DMF and DMSO at a molar ratio of 0.95:0.05:1 to form a 1.6M CsI solution. 0.05 FA 0.95 The PbI3 solution contained DMF and DMSO in a volume ratio of 4:1. In this comparative example, the Cs... 0.05 FA 0.95 PbI3 solution is the perovskite precursor solution.

[0060] Comparative Example 2:

[0061] This comparative example provides a photovoltaic energy storage system, specifically comprising three perovskite solar cells and two aqueous vanadium-based zinc-ion batteries.

[0062] The preparation method of the perovskite precursor solution in this comparative example is the same as that in Comparative Example 1.

[0063] Example 1:

[0064] This embodiment provides a photovoltaic energy storage system, specifically including two perovskite solar cells and one aqueous vanadium-based zinc-ion battery.

[0065] In this embodiment, the perovskite precursor solution is prepared by dissolving FAI, CsI, and PbI2 in a mixed solvent of DMF and DMSO at a molar ratio of 0.95:0.05:1 to form a 1.6M CsI solution. 0.05 FA 0.95 A PbI3 solution in which the volume ratio of DMF to DMSO is 4:1; 1 mL of Cs was taken. 0.05 FA 0.95 A PbI3 solution was mixed with 2 μL of 2-thiophenecarboxyl chloride to obtain a perovskite precursor solution. That is, in this embodiment, the perovskite precursor solution is Cs. 0.05 FA 0.95 A mixture of PbI3 solution and 2-thiophenecarboxyl chloride.

[0066] Example 2:

[0067] This embodiment provides a photovoltaic energy storage system, including three perovskite solar cells and two aqueous vanadium-based zinc-ion batteries.

[0068] In this embodiment, the preparation method of the perovskite precursor solution is the same as in Example 1.

[0069] Table 1 shows the relevant data of the perovskite solar cells and photovoltaic energy storage systems in Comparative Example 1, Comparative Example 2, Example 1, and Example 2. The testing equipment used to obtain the relevant data was a Keithley 2400 and a Newport Solar Simulator 3A (test conditions: AM1.5, 100 mW / cm²). 2 ), CHI 650D, Neware Battery Performance Analyzer. In Table 1, J SC V represents the short-circuit current density of a perovskite solar cell. OC is the open-circuit voltage of the perovskite solar cell, FF is the fill factor of the perovskite solar cell, PCE is the photoelectric conversion efficiency of the perovskite solar cell, and E is the open-circuit voltage of the perovskite solar cell. discharge η represents the total electrical energy that can be released when all aqueous vanadium-based zinc-ion batteries in a photovoltaic energy storage system are fully charged. overall The total energy conversion efficiency of a photovoltaic energy storage system is the ratio between the total electrical energy that can be released after all aqueous vanadium-based zinc-ion batteries in the photovoltaic energy storage system are fully charged and the total light energy received by all perovskite solar cells in the photovoltaic energy storage system.

[0070] Table 1

[0071]

[0072] First, comparing Comparative Example 1 and Example 1 reveals that, in the case of a photovoltaic energy storage system comprising two perovskite solar cells and one aqueous vanadium-based zinc-ion battery, modifying the perovskite layer with 2-thiophenecarboxyl chloride can not only improve the photoelectric conversion efficiency of the perovskite solar cells themselves, but also improve the overall energy conversion efficiency of the photovoltaic energy storage system.

[0073] Secondly, comparing Comparative Example 2 and Example 2 reveals that, in the case of a photovoltaic energy storage system including three perovskite solar cells and two aqueous vanadium-based zinc-ion cells, modifying the perovskite layer with 2-thiophenecarboxyl chloride can simultaneously improve the photoelectric conversion efficiency of the perovskite solar cells and the total energy conversion efficiency of the photovoltaic energy storage system.

[0074] This confirms that the modification effect of 2-thiophenecarboxyl chloride on the perovskite layer can improve the overall energy conversion efficiency of the photovoltaic energy storage system.

[0075] Further comparison of Comparative Example 1 and Comparative Example 2 reveals that, without modification by 2-thiophene carboxyl chloride, the photoelectric conversion efficiency of perovskite solar cells can be improved with the increase in the number of perovskite solar cells and aqueous vanadium-based zinc-ion cells in the photovoltaic energy storage system; however, the overall energy conversion efficiency of the photovoltaic energy storage system remains almost unchanged.

[0076] Conversely, by comparing Example 1 and Example 2, it can be found that after modifying the perovskite layer with 2-thiophenecarboxyl chloride, as the number of perovskite solar cells and aqueous vanadium-based zinc-ion cells in the photovoltaic energy storage system increases, although the photoelectric conversion efficiency of the perovskite solar cells decreases, the total energy conversion efficiency of the photovoltaic energy storage system is significantly improved.

[0077] This confirms that only after the perovskite layer is modified by 2-thiophenecarboxyl chloride can the photovoltaic energy storage system further improve its total energy conversion efficiency by increasing the number of perovskite solar cells and aqueous vanadium-zinc ion cells. In other words, based on the modification effect of 2-thiophenecarboxyl chloride on the perovskite layer, the number of means to improve the total energy conversion efficiency of the photovoltaic energy storage system can be increased, thereby enabling a more significant improvement in the total energy conversion efficiency of the photovoltaic energy storage system.

[0078] See details Figure 1 and Figure 2 Pb 4f in the perovskite layer of Comparative Example 1 5 / 2and Pb 4f 7 / 2 The characteristic peaks are located at 143.30 eV and 138.42 eV, respectively, while in Example 1, Pb 4f 5 / 2 and Pb 4f 7 / 2 The characteristic peaks shifted to 143.18 eV and 138.30 eV, respectively, which may be due to uncoordinated Pb in the perovskite layer. 2+ It interacts with the C=O bond in 2-thiophenecarboxyl chloride; I 3d in the perovskite layer of Comparative Example 1 3 / 2 and I 3d 5 / 2 The characteristic peaks are located at 630.97 eV and 619.52 eV, respectively, while in Example 1, I 3d 3 / 2 and I 3d 5 / 2 The characteristic peaks shifted to lower values ​​of 630.76 eV and 619.31 eV, respectively, indicating that iodine defects in the perovskite layer may be passivated by Cl⁻ in 2-thiophenecarboxylic acid chloride. This suggests that 2-thiophenecarboxylic acid chloride may improve the photoelectric conversion efficiency of perovskite solar cells by enhancing the thin film quality of the perovskite layer.

[0079] See Figure 3 Compared with Comparative Example 1, in Example 1, the energy shift between the perovskite layer and the PCBM was significantly reduced after modification with 2-thiophenecarboxyl chloride, which is beneficial for electron transfer and suppresses charge accumulation at the interface, thereby improving device performance.

[0080] See Figure 4 During the photocharging process, the output power of the perovskite solar cell in Example 1 is significantly improved compared to Comparative Example 1. Since the photovoltaic energy storage systems in Example 1 and Comparative Example 1 have roughly the same capacity, the charging time required for the photovoltaic energy storage system in Example 1 to reach full charge is shorter. In other words, the photovoltaic energy storage system in Example 1 requires less light energy to reach full charge, meaning that the overall energy conversion efficiency of the photovoltaic energy storage system in Example 1 is improved compared to Comparative Example 1. Similarly, as... Figure 5 As shown, in Example 2, the overall energy conversion efficiency of the photovoltaic energy storage system was also improved compared to Comparative Example 2. This conclusion matches the data in Table 1.

[0081] Comparative Example 3:

[0082] This comparative example provides a perovskite solar cell that is not connected to an aqueous vanadium-based zinc-ion battery, nor is it assembled into a photovoltaic energy storage system.

[0083] In this comparative example, the perovskite precursor solution was prepared by dissolving FAI (formamidinium iodide), CsI, and PbI2 in a mixed solvent of DMF and DMSO at a molar ratio of 0.95:0.05:1 to form a 1.6M CsI solution.0.05 FA 0.95 The PbI3 solution contained DMF and DMSO in a volume ratio of 4:1. In this comparative example, the Cs... 0.05 FA 0.95 PbI3 solution is the perovskite precursor solution.

[0084] Example 3:

[0085] This embodiment provides a perovskite solar cell that is not connected to an aqueous vanadium-based zinc-ion battery, nor is it assembled into a photovoltaic energy storage system.

[0086] In this embodiment, the perovskite precursor solution is prepared by dissolving FAI, CsI, and PbI2 in a mixed solvent of DMF and DMSO at a molar ratio of 0.95:0.05:1 to form a 1.6M CsI solution. 0.05 FA 0.95 A PbI3 solution with a DMF to DMSO volume ratio of 4:1 was prepared. 1 mL of Cs was then taken. 0.05 FA 0.95 A PbI3 solution was mixed with 1 μL of 2-thiophenecarboxyl chloride to obtain a perovskite precursor solution.

[0087] Example 4:

[0088] This embodiment provides a perovskite solar cell that is not connected to an aqueous vanadium-based zinc-ion battery, nor is it assembled into a photovoltaic energy storage system.

[0089] In this embodiment, the perovskite precursor solution is prepared by dissolving FAI, CsI, and PbI2 in a mixed solvent of DMF and DMSO at a molar ratio of 0.95:0.05:1 to form a 1.6M CsI solution. 0.05 FA 0.95 A PbI3 solution with a DMF to DMSO volume ratio of 4:1 was prepared. 1 mL of Cs was then taken. 0.05 FA 0.95 A PbI3 solution was mixed with 2 μL of 2-thiophenecarboxyl chloride to obtain a perovskite precursor solution.

[0090] Example 5:

[0091] This embodiment provides a perovskite solar cell that is not connected to an aqueous vanadium-based zinc-ion battery, nor is it assembled into a photovoltaic energy storage system.

[0092] In this embodiment, the perovskite precursor solution is prepared by dissolving FAI, CsI, and PbI2 in a mixed solvent of DMF and DMSO at a molar ratio of 0.95:0.05:1 to form a 1.6M CsI solution. 0.05 FA 0.95A PbI3 solution with a DMF to DMSO volume ratio of 4:1 was prepared. 1 mL of Cs was then taken. 0.05 FA 0.95 A PbI3 solution was mixed with 4 μL of 2-thiophenecarboxyl chloride to obtain a perovskite precursor solution.

[0093] pass Figures 6-9 It can be confirmed that modifying the perovskite layer with a small amount of 2-thiophenecarboxyl chloride can improve the film quality of the perovskite layer to a certain extent, which is consistent with the aforementioned conclusion. However, when excessive 2-thiophenecarboxyl chloride is used to modify the perovskite layer, it will lead to damage to the perovskite layer.

[0094] The photoelectric data of the perovskite solar cells in Comparative Example 3 and Examples 3-5 are shown in Table 2.

[0095] Table 2

[0096]

[0097] and Figures 6-9 Correspondingly, after modifying the perovskite layer with a small amount of 2-thiophenecarboxyl chloride, the photoelectric conversion efficiency of the perovskite solar cell was improved compared with Comparative Example 3. However, when excessive 2-thiophenecarboxyl chloride was used to modify the perovskite layer, the photoelectric conversion efficiency of the perovskite solar cell decreased, and even fell below that of Comparative Example 3.

[0098] The technical features of the above embodiments can be combined arbitrarily. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as the combination of these technical features does not contradict each other, it should be considered within the scope of this specification. The above embodiments only illustrate several implementation methods of the present invention, and their descriptions are relatively specific and detailed, but they should not be construed as limiting the scope of the invention patent. It should be noted that for those skilled in the art, several modifications and improvements can be made without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A perovskite precursor solution, characterized in that, Including Cs 0.05 FA 0.95 PbI3 and 2-thiophenecarboxyl chloride.

2. The perovskite precursor solution according to claim 1, characterized in that, In the perovskite precursor solution, Cs 0.05 FA 0.95 The ratio between the amount of PbI3 and the volume of 2-thiophenecarboxyl chloride is 1.6 × 10⁻⁶. -3 mol: 2μL.

3. A perovskite solar cell, comprising a conductive glass layer, a hole transport layer, a perovskite layer, an electron transport layer, and an electrode layer arranged sequentially in layers, characterized in that, The perovskite layer is obtained by spin coating with the perovskite precursor liquid as described in claim 1 or 2.

4. A photovoltaic energy storage system, comprising a photovoltaic module and a charging module connected in series with the photovoltaic module, wherein the charging module comprises at least one aqueous vanadium-based zinc-ion battery, characterized in that, The photovoltaic module includes at least two perovskite solar cells as described in claim 3, connected in series.

5. The photovoltaic energy storage system according to claim 4, characterized in that, The method for preparing the positive electrode sheet in the aqueous vanadium-based zinc-ion battery includes: 0.546 g of vanadium pentoxide, 4 mL of hydrogen peroxide, 0.3 mmol of strontium acetate, and 0.1 mL of 3,4-ethylenedioxythiophene were added to 70 mL of deionized water and then reacted in a reactor at 180 °C for 4 hours to obtain a positive electrode slurry. The positive electrode slurry is coated onto the current collector, and then dried, rolled and punched to obtain the positive electrode sheet; In the aforementioned aqueous vanadium-based zinc-ion battery, the negative electrode is zinc foil, the separator is a glass fiber membrane, the solute of the electrolyte is zinc trifluoromethanesulfonate, and the solvent of the electrolyte is water.

6. The photovoltaic energy storage system according to claim 5, characterized in that, The method for preparing the perovskite solar cell includes: A 5 mg / mL nickel oxide aqueous solution was spin-coated onto a conductive glass layer and then dried at 150 °C to obtain the hole transport layer. The spin-coating speed of the nickel oxide aqueous solution was 4000 rpm and the spin-coating time was 30 s. FAI, CsI, and PbI₂ were dissolved in a mixed solvent of DMF and DMSO at a molar ratio of 0.95:0.05:1 to form a 1.6 M CsI solution. 0.05 FA 0.95 A PbI3 solution in which the volume ratio of DMF to DMSO is 4:1; Take 1 mL of Cs 0.05 FA 0.95 PbI3 solution and 2 μL of 2-thiophenecarboxyl chloride were mixed to obtain perovskite precursor solution; The perovskite precursor solution is spin-coated onto the hole transport layer and then annealed at 150°C to obtain the perovskite layer; wherein the spin-coating speed of the perovskite precursor solution is 4000 rpm and the spin-coating time is 30 s, and chlorobenzene is added dropwise during the spin-coating process of the perovskite precursor solution. A chlorobenzene solution of PCBM was spin-coated onto the perovskite layer to obtain an electron transport layer, wherein the concentration of PCBM was 30 mg / mL, the spin-coating speed of the chlorobenzene solution of PCBM was 3000 rpm, and the spin-coating time was 30 s. A 100 nm thick layer of silver is deposited on the electron transport layer to obtain an electrode layer.

7. The photovoltaic energy storage system according to claim 6, characterized in that, The number of perovskite solar cells is three, and the number of aqueous vanadium-based zinc-ion cells is two.

8. A method for fabricating a perovskite solar cell, characterized in that, include: An aqueous solution of nickel oxide is spin-coated onto a conductive glass layer and then dried to obtain a hole transport layer. The perovskite precursor liquid as described in claim 1 or 2 is spin-coated onto the hole transport layer, and then annealed to obtain the perovskite layer. A chlorobenzene solution of PCBM is spin-coated onto the perovskite layer to obtain an electron transport layer; Silver is deposited on the electron transport layer to obtain the electrode layer.

9. The method for preparing a perovskite solar cell according to claim 8, characterized in that, The concentration of the nickel oxide aqueous solution is 5 mg / mL, the spin coating speed of the nickel oxide aqueous solution is 4000 rpm, the spin coating time is 30 s, and the drying temperature is 150℃. The spin coating speed of the perovskite precursor solution is 4000 rpm and the spin coating time is 30 s. Chlorobenzene is added dropwise during the spin coating process of the perovskite precursor solution. The concentration of the chlorobenzene solution in the PCBM is 30 mg / mL, the spin coating speed of the chlorobenzene solution in the PCBM is 3000 rpm, and the spin coating time is 30 s. The thickness of the electrode layer is 100 nm; The preparation method of the perovskite precursor solution includes: dissolving FAI, CsI, and PbI2 in a mixed solvent of DMF and DMSO at a molar ratio of 0.95:0.05:1 to form a CsI solution with a concentration of 1.6M. 0.05 FA 0.95 A PbI3 solution in which the volume ratio of DMF to DMSO is 4:1; Take 1 mL of Cs 0.05 FA 0.95 A PbI3 solution was mixed with 2 μL of 2-thiophenecarboxyl chloride to obtain a perovskite precursor solution. Application of 10,2-thiophenecarboxyl chloride in improving the photoelectric conversion efficiency of perovskite solar cells and / or the total energy conversion efficiency of photovoltaic energy storage systems.

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