Hydrazine-based phenyl phosphite additive modified perovskite solar cell and preparation method and application thereof

Abstract

The application discloses a hydrazine-based phenyl phosphite additive modified perovskite solar cell and a preparation method and application thereof, and belongs to the technical field of photovoltaic solar materials. The hydrazine-based phenyl phosphite is used as a perovskite solar cell additive. The hydrazine-based phenyl phosphite small molecule has an electron-donating group (hydrazine group) and an electron-withdrawing group (phosphoric acid group). The phosphoric acid group forms coordination with Pb 2+ , the N-H bond in the hydrazine group forms a hydrogen bond with a halogen ion, and the two groups synergistically passivate Pb 2+ , Pb 0 and halogen ion vacancies through coordination and hydrogen bond, thereby significantly reducing non-radiative recombination. The application balances the strength of covalent and non-covalent interactions, reduces defects of a perovskite crystal phase, induces better growth of the perovskite crystal, suppresses carrier recombination in the perovskite, and improves photoelectric conversion efficiency and stability of the device.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of photovoltaic solar materials, and particularly relates to a hydrazine-based benzene phosphite additive modified perovskite solar cell and a preparation method and application thereof. BACKGROUND

[0002] With the global energy structure accelerating the transformation to low carbonization, new energy technology has become the intersection focus of semiconductor material science and clean energy revolution. Under the background of the deep integration of new energy and semiconductor technology, perovskite material, as the core of the third generation of semiconductor technology, has become a research hotspot in the photovoltaic field due to its unique organic-inorganic hybrid semiconductor characteristics (band gap adjustable range 1.2~2.3eV, carrier mobility >10cm 2 / V·s and longer exciton diffusion length). The demand for high-efficiency and low-cost semiconductor devices is increasingly urgent in the new energy industry (such as solar power generation), and perovskite semiconductor material can greatly reduce the average levelized cost of electricity (LCOE) by 40% or more due to its low-temperature process (<150℃) and theoretical photoelectric conversion efficiency of up to 33% (significantly exceeding the 29.4% limit of crystalline silicon semiconductor), which is regarded as a key path to break through the bottleneck of traditional silicon-based semiconductor photovoltaic technology.

[0003] However, in the large-scale application scenario of new energy, the photoelectric conversion efficiency, stability and safety bottleneck of perovskite semiconductor devices need to be broken through. Although the increasingly prominent perovskite solar cell has excellent device performance, low device preparation cost and can be prepared by solution method, due to the limitation of material structure and properties, water, oxygen, light and heat can all cause the material to decompose. Therefore, the long-term running stability of perovskite solar cell under high efficiency conditions has not been realized, which is still a key obstacle that needs to be overcome before full marketization. In addition, for perovskite solar cells prepared from lead halide, lead halide has higher water solubility (K sp >10 -8 ) in rainwater. The leakage of lead is harmful to biology and environment. Therefore, it is necessary to use appropriate materials to optimize the quality of perovskite thin film, which can effectively delay the degradation process of perovskite thin film, inhibit the leakage of lead and improve the comprehensive performance of the device, realizing the synergistic optimization of new energy device efficiency-life-environment friendliness.

[0004] The prior art discloses a high-efficiency tin-lead alloy perovskite solar cell prepared by using 4-hydrazine benzoic acid as an additive. 4-hydrazine benzoic acid is used to inhibit the oxidation of Sn 2+ , and at the same time passivate perovskite defects. The photoelectric conversion efficiency of the cell is 18.58%~20.49%, and the photoelectric efficiency still needs to be improved. SUMMARY

[0005] To solve the problems existing in the prior art, the primary object of the present application is to provide application of hydrazinobenzenephosphorous acid as an additive for perovskite solar cells.

[0006] Another object of the present application is to provide application of hydrazinobenzenephosphorous acid as an additive for perovskite solar cell perovskite layers.

[0007] Another object of the present application is to provide a perovskite solar cell.

[0008] Another object of the present application is to provide a preparation method of a perovskite solar cell.

[0009] Another object of the present application is to provide application of a perovskite solar cell in preparation of a photovoltaic power generation device.

[0010] To achieve the above objects, the present application provides the following technical solutions.

[0011] Application of hydrazinobenzenephosphorous acid as an additive for perovskite solar cells.

[0012] Application of hydrazinobenzenephosphorous acid as an additive for perovskite solar cell perovskite layers.

[0013] The present application uses hydrazinobenzenephosphorous acid as an additive for perovskite solar cells, and the phosphoric acid in the hydrazinobenzenephosphorous acid can induce grain growth, and the O=P group in the phosphoric acid group can coordinate with Pb 2+ , thereby forming an adduct, inducing and strengthening the interaction between adjacent perovskite crystals, making the perovskite crystals grow better, passivating the defects in the perovskite layer, reducing carrier loss, and further improving the open-circuit voltage of the perovskite solar cell.

[0014] Due to the addition of excessive lead iodide in the perovskite layer and the degradation of lead iodide, Pb 0 defects are easily formed in the perovskite crystal, which can significantly increase carrier recombination, reduce device efficiency and stability, and the phosphoric acid group can convert Pb 0 into Pb 2+ and stabilize Pb 2+ through coordination, thereby inhibiting lead iodide degradation or covering the Pb 0 surface by adsorption, thereby inhibiting Pb 0 from becoming a carrier recombination center.

[0015] The strong coordination of the phosphoric acid group in the hydrazinobenzenephosphorous acid with Pb 2+ can inhibit Pb2+ The transfer of the lead makes it have excellent lead fixation ability, thereby inhibiting the leakage of lead ions.

[0016] A method for improving the photoelectric efficiency of a perovskite solar cell, hydrazinobenzene phosphinic acid is added to a perovskite precursor solution.

[0017] Specifically, the concentration of hydrazinobenzene phosphinic acid in the perovskite precursor solution is 0.1-0.3 mg / mL.

[0018] Preferably, the concentration of hydrazinobenzene phosphinic acid in the perovskite precursor solution is 0.15-0.25 mg / mL.

[0019] Specifically, the solvent of the hydrazinobenzene phosphinic acid solution is at least one of DMSO, DMF, and ACN.

[0020] A perovskite solar cell additive, comprising: hydrazinobenzene phosphinic acid.

[0021] A perovskite solar cell, the device structure from bottom to top is conductive glass layer, hole transport layer, perovskite layer, electron transport layer and metal electrode layer in turn, and the perovskite layer contains hydrazinobenzene phosphinic acid.

[0022] Specifically, the conductive glass layer is one of ITO conductive glass or FTO conductive glass.

[0023] Specifically, the hole transport layer is at least one of PTAA, MeO-2PACz, and Me-2PACz.

[0024] Specifically, the perovskite layer comprises formamidinium hydrohalide, alkylammonium halide, cesium halide, and lead halide.

[0025] More specifically, the formamidinium halide is at least one of formamidinium hydrochloride, formamidinium hydrobromide, and formamidinium hydroiodide.

[0026] More specifically, the alkylammonium halide is at least one of methylammonium iodide, methylammonium chloride, and methylammonium bromide.

[0027] More specifically, the cesium halide is at least one of cesium iodide, cesium chloride, and cesium bromide.

[0028] More specifically, the lead halide is at least one of lead iodide, lead chloride, and lead bromide.

[0029] Preferably, the perovskite layer comprises formamidinium hydroiodide, methylammonium chloride, methylammonium iodide, cesium iodide, and lead iodide.

[0030] Specifically, the thickness of the perovskite layer is 680-720 nm.

[0031] Specifically, the material of the electron transport layer is a carbon 60 derivative.

[0032] More specifically, the carbon 60 derivative is at least one of [6,6]-phenyl C61 butyric acid methyl ester, [6,6]-thiophene C61 butyric acid methyl ester, [6,6]-phenyl-C61-butyric acid n-octyl ester or [6,6]-phenyl-C61-butyric acid dodecyl ester.

[0033] A preparation method of a perovskite solar cell, comprising: sequentially preparing a hole transport layer, a perovskite layer, an electron transport layer and a metal electrode layer on a conductive glass layer by a spin coating method, and the preparation method of the perovskite layer comprises the following steps:

[0034] S1. mixing hydrazinobenzene phosphorous acid with a perovskite solution to obtain a first perovskite precursor solution,

[0035] S2. spin coating the first perovskite precursor solution and heating to obtain the perovskite layer.

[0036] Specifically, the active components in the perovskite precursor solution include formamidinium hydriodide, alkyl ammonium halide, cesium halide and lead halide.

[0037] The active components in the perovskite precursor solution are non-solvent components and do not include additives.

[0038] Preferably, the active components in the perovskite precursor solution include formamidinium hydriodide, methyl ammonium chloride, methyl ammonium iodide, cesium iodide and lead iodide.

[0039] Preferably, the chemical formula of the active components in the perovskite precursor solution is Cs x (FA y MA 1-y ) 1-x PbI3, wherein 0

[0040] Specifically, the ratio of the total mass of the active components in the perovskite precursor solution to the mass of hydrazinobenzene phosphorous acid is (1100-1150):(0.1-0.3).

[0041] More specifically, the ratio of the total mass of the active components in the perovskite precursor solution to the mass of hydrazinobenzene phosphorous acid is 1122:(0.1-0.3).

[0042] Specifically, in the step S1, the mixing time is 12-18 hours.

[0043] Specifically, the solvent of the first perovskite precursor is at least one of DMF, DMSO and ACN.

[0044] Specifically, in the step S2, the spin-coating rotation speed is 3500-4500 rpm.

[0045] Specifically, in the step S2, the spin-coating time is 20-40 seconds.

[0046] Specifically, in the step S2, the heating annealing temperature is 80-120 DEG C.

[0047] Specifically, in the step S2, the heating annealing time is 10-50 minutes.

[0048] The application also protects the application of the above-mentioned perovskite solar cell in the preparation of photovoltaic power generation equipment.

[0049] Compared with the prior art, the application has the following beneficial effects:

[0050] The application adopts hydrazinobenzene phosphorous acid as a perovskite solar cell additive, and the hydrazinobenzene phosphorous acid small molecule has an electron-donating group (hydrazine group) and an electron-withdrawing group (phosphoric acid group). 2+ The phosphoric acid group forms coordination, and the N-H bond in the hydrazine group forms a hydrogen bond with the halogen ion, and the two groups passivate Pb 2+ , Pb 0 and halogen ion vacancies through coordination and hydrogen bonding, significantly reducing non-radiative recombination. The application balances the strong and weak interactions of covalence and non-covalence, reduces the defects of the perovskite crystal phase, and induces better growth of the perovskite crystal, inhibits the carrier recombination in the perovskite, improves the photoelectric conversion efficiency and stability of the device, and effectively inhibits the leakage of lead ions in the perovskite solar cell. BRIEF DESCRIPTION OF DRAWINGS

[0051] Figure 1 The J-V curve of the perovskite solar cell of the example and the comparative example.

[0052] Figure 2 The molecular structure diagram of the hydrazinobenzene phosphorous acid.

[0053] Figure 3 The steady-state photoluminescence (PL) spectrum of the perovskite layer of Example 3 and Comparative Example 1.

[0054] Figure 4 The time-resolved photoluminescence (TRPL) spectrum of the perovskite layer of Example 3 and Comparative Example 1.

[0055] Figure 5 The XRD diagram of Example 3 and Comparative Example 1.

[0056] Figure 6 The UV-Vis diagram (left side) and Tauc diagram (right side) of Example 3 and Comparative Example 1.

[0057] Figure 7 SEM images of Example 3 and Comparative Example 1.

[0058] Figure 8 Normalized efficiency-time curve of Example 3 and Comparative Example 1.

[0059] Figure 9 Lead leakage amount curve and device water immersion experiment graph of Example 3 and Comparative Example 1. DETAILED DESCRIPTION

[0060] The application is further described below in conjunction with examples. These examples are only used to illustrate the application and are not used to limit the scope of the application. The experimental methods in the following example are not specified, and are generally carried out according to conventional conditions in the art or according to the conditions recommended by the manufacturer; the raw materials, reagents, etc. used, if not specifically stated, are commercially available raw materials and reagents. Any non-essential changes and substitutions made by those skilled in the art on the basis of the present application are within the scope of the present application.

[0061] A perovskite solar cell additive, the preparation method thereof comprises the following steps:

[0062] 2mg hydrazinobenzene phosphite is added to 1mL DMSO, and magnetic stirring is carried out at 60℃ for 60 minutes to form a hydrazinobenzene phosphite solution with a concentration of 2.0mg / mL, thereby obtaining the perovskite solar cell additive.

[0063] The chemical formula of the active component in the perovskite precursor solution in the examples and comparative examples is Cs 0.05 (FA 0.8 MA 0.2 ) 0.95 PbI3.

[0064] Example 1

[0065] The present embodiment provides a perovskite solar cell, and the device structure is sequentially from bottom to top: a conductive glass layer, a hole transport layer, a perovskite layer, an electron transport layer and a metal electrode layer. The preparation method comprises the following steps:

[0066] S1. The ITO conductive glass is sequentially ultrasonically cleaned in deionized water, acetone and isopropanol for 15 minutes, dried with nitrogen, and subjected to ultraviolet ozone treatment in an ultraviolet ozone cleaning machine; after cleaning, it is quickly transferred to a nitrogen atmosphere glove box, and then a hole transport layer PTAA is spin-coated on the ITO substrate, the spin-coating speed is set to 3000rpm, the spin-coating time is 30 seconds, 20 microliters of PTAA is added dropwise on the ITO substrate at 25 seconds, and after spin-coating, it is transferred to a heating table at 100℃ for heating for 10 minutes to obtain a hole transport layer;

[0067] S2.1 Dissolve formamidinium hydriodide, methylammonium chloride, methylammonium iodide, cesium iodide and lead iodide in DMF and DMSO, add 0.05 ml of hydrazinobenzene phosphinic acid solution with a concentration of 2.0 mg / ml (i.e. perovskite solar cell additive), magnetically stir for 15 hours to obtain a perovskite precursor solution; the concentration of hydrazinobenzene phosphinic acid in the perovskite precursor solution is 0.1 mg / mL; the ratio of the total mass of active components in the perovskite precursor solution to the mass of hydrazinobenzene phosphinic acid is 1122:0.1.

[0068] S2.2 Drop the perovskite precursor solution on the PTAA modified ITO substrate, set the rotation speed of spin coating to 4000 rpm, the spin coating time to 35 seconds, and drop the anti-solvent toluene at 10 seconds, then transfer to a heating table for heating annealing, the temperature is 100℃, and the time is 30 minutes, to form a perovskite film on the PTAA modified ITO substrate, and obtain a perovskite layer;

[0069] S3. Dissolve 23 mg of [6,6]-phenyl C 61 PCBM electronic transport layer solution is prepared by dissolving 23 mg of [6,6]-phenyl C 61 PCBM electronic transport layer solution is prepared by dissolving 23 mg of [6,6]-phenyl C 61 PCBM electronic transport layer solution is prepared by dissolving 23 mg of [6,6]-phenyl C 61 PCBM electronic transport layer solution is prepared by dissolving 23 mg of [6,6]-phenyl C 61 PCBM electronic transport layer solution is prepared by dissolving 23 mg of [6,6]-phenyl C

[0070] S4. Put the device prepared in step S3 into a vacuum coating machine, vacuumize, then put a silver metal source into a tungsten boat, evaporate silver electrode to obtain a metal electrode layer; after assembly, a perovskite solar cell is obtained.

[0071] Example 2

[0072] The difference between this embodiment and example 1 is that in step S2.1, 0.075 ml of hydrazinobenzene phosphinic acid solution with a concentration of 2.0 mg / ml is added, and the concentration of hydrazinobenzene phosphinic acid in the perovskite precursor solution is 0.15 mg / mL; the ratio of the total mass of active components in the perovskite precursor solution to the mass of hydrazinobenzene phosphinic acid is 1122:0.15.

[0073] Example 3

[0074] The difference between this example and Example 1 is that in step S2.1, 0.10 ml of hydrazinobenzenephosphinic acid solution with a concentration of 2.0 mg / ml is added, and the concentration of hydrazinobenzenephosphinic acid in the perovskite precursor solution is 0.2 mg / mL; the ratio of the total mass of active components in the perovskite precursor solution to the mass of hydrazinobenzenephosphinic acid is 1122:0.2.

[0075] Example 4

[0076] The difference between this example and Example 1 is that in step S2.1, 0.125 ml of hydrazinobenzenephosphinic acid solution with a concentration of 2.0 mg / ml is added, and the concentration of hydrazinobenzenephosphinic acid in the perovskite precursor solution is 0.25 mg / mL; the ratio of the total mass of active components in the perovskite precursor solution to the mass of hydrazinobenzenephosphinic acid is 1122:0.25.

[0077] Example 5

[0078] The difference between this example and Example 1 is that in step S2.1, 0.15 ml of hydrazinobenzenephosphinic acid solution with a concentration of 2.0 mg / ml is added, and the concentration of hydrazinobenzenephosphinic acid in the perovskite precursor solution is 0.3 mg / mL; the ratio of the total mass of active components in the perovskite precursor solution to the mass of hydrazinobenzenephosphinic acid is 1122:0.3.

[0079] Comparative Example 1

[0080] The difference between this comparative example and Example 1 is that no hydrazinobenzenephosphinic acid is added to the first perovskite precursor solution, and the rest is the same as Example 1.

[0081] Comparative Example 2

[0082] The difference between this comparative example and Example 1 is that hydrazinobenzenephosphinic acid is replaced by hydrazinobenzoic acid.

[0083] Comparative Example 3

[0084] The difference between this comparative example and Example 3 is that hydrazinobenzenephosphinic acid is replaced by hydrazinobenzenephosphinate hydrochloride.

[0085] Performance Test

[0086] Current density-voltage (J-V) characteristic curve test: the performance of the device is evaluated by measuring the J-V characteristic curve. The experiment uses a solar simulator to provide AM 1.5G, 100 mW·cm -2 of radiation light, and the J-V characteristic curve can be obtained by applying a bias voltage across the test cell and measuring the current of its external circuit using a Keithley 2400C digital source meter, and the effective area of the device is 0.04 cm 2 .

[0087] Steady-state photoluminescence (PL) emission spectra characterization test: The sample was prepared on quartz or glass as a substrate. The sample was spin-coated on the transparent conductive glass to form a perovskite layer to prepare a complete sample. When testing steady-state PL, a xenon lamp was used as the excitation light source. When testing transient PL, another excitation light source was used. When fitting the transient PL lifetime, a double exponential fitting method was used, and the fitting index χ 2 was about 1 to ensure the reliability of the fitting.

[0088] X-ray diffraction (XRD) characterization test: The sample was prepared on quartz or glass as a substrate. The sample was spin-coated on the transparent conductive glass to form a perovskite layer to prepare a complete sample. The scanning angle was 10-45°. The effect of hydrazinobenzene phosphorous acid on the crystallinity of the perovskite film was studied.

[0089] Ultraviolet absorption (UV-Vis) spectroscopy characterization test: The sample was prepared on quartz or glass as a substrate. The sample was spin-coated on the transparent conductive glass to form a perovskite layer to prepare a complete sample. The scanning range was 300-800 nm. The effect of hydrazinobenzene phosphorous acid on the photoelectric properties of the perovskite film was studied.

[0090] Field emission electron scanning (SEM) microscope characterization test: The sample was prepared on quartz or glass as a substrate. The sample was spin-coated on the transparent conductive glass to form a perovskite layer to prepare a complete sample. The cross-sectional sample was cut from the smooth back of the quartz or glass sample with a glass knife to obtain a flat sample.

[0091] Normalized efficiency-time curve test: The unsealed and complete perovskite solar photovoltaic device was placed in a glove box at room temperature (25±2°C) in a nitrogen atmosphere, and the J-V device test was completed regularly.

[0092] Device immersion test: The unsealed and complete perovskite solar photovoltaic device was placed in 50 ml of distilled water at 25°C, and then 2.5 ml of water was taken as a sample every certain period of time, and the content of lead element in the water was quantitatively analyzed by measuring the degree of absorption of the characteristic light by the lead element atomic vapor in the sample using atomic flame absorption (FAAs) method.

[0093] The experimental results are shown below:

[0094] Figure 1 The J-V curve of the perovskite solar cell of the example and the comparative example is shown. The results are shown in Table 1.

[0095] Table 1 J-V test results of the perovskite solar cell of the example and the comparative example

[0096]

[0097] As can be seen from Table 1, the photoelectric conversion efficiency of the perovskite solar device using hydrazinobenzenephosphonic acid as an additive is generally better than that of the perovskite solar device without adding an additive (i.e. Comparative Example 1) and that of the perovskite solar device using hydrazinobenzoic acid as an additive (i.e. Comparative Example 2), indicating that hydrazinobenzenephosphonic acid has a significant effect on improving the efficiency of the perovskite device.

[0098] As can be seen from Example 1 and Comparative Example 2, the photoelectric conversion efficiency of the perovskite solar cell of Comparative Example 2 is lower than that of Example 1. This indicates that the phosphonic group in hydrazinobenzenephosphonic acid has a much stronger passivation effect on the perovskite layer than the carboxyl group in hydrazinobenzoic acid.

[0099] As can be seen from Example 3 and Comparative Example 3, the photoelectric conversion efficiency of the perovskite solar cell of Comparative Example 3 is lower than that of Example 3. This indicates that the phosphonic group in hydrazinobenzenephosphonic acid has a much stronger passivation effect on the perovskite layer than the passivation effect of hydrazinobenzenephosphonic acid on the perovskite layer. This is because pure hydrazinobenzenephosphonic acid does not contain Cl - , and the benzenephosphonic group coordinates with Pb 2+ through the phosphonic group, forming more uniform nucleation sites and promoting the formation of dense, large-grained perovskite films. The introduction of Cl - in hydrazinobenzenephosphonic acid hydrochloride prolongs the nucleation time of perovskite, leading to uneven grain size distribution and increasing the density of grain boundary defects. Cl - is difficult to completely volatilize during annealing, and the unvolatilized Cl - may remain in the grain boundary or lattice, forming ion migration channels or recombination centers, reducing device efficiency. In addition, due to the size difference between Cl - and I - , the introduction of Cl - may weaken the hydrogen bond network and reduce the passivation effect.

[0100] Figure 3 The steady-state photoluminescence (PL) spectrum of the perovskite layer of Example 3 and Comparative Example 1 is shown in the figure. As can be seen from the figure, the fluorescence peak emission intensity of Example 3 is stronger than that of Comparative Example 1, indicating that the addition of hydrazinobenzenephosphonic acid produces more carriers under photoexcitation of the perovskite film, effectively reducing non-radiative recombination caused by defects in the perovskite layer. Figure 4The time-resolved photoluminescence (TRPL) spectra of the perovskite layers of Example 3 and Comparative Example 1 are shown in the figure. The fluorescence lifetime curve of the perovskite intrinsic layer of Example 3 is higher than that of Comparative Example 1, indicating that the perovskite thin film lifetime is prolonged in Example 3. This is because the hydrazine phenyl phosphite as a perovskite solar cell additive can reduce the grain boundary defects and has a better defect passivation effect, which can effectively reduce the non-radiative recombination and loss of photo-generated carriers at defects.

[0101] Figure 5 The XRD patterns of Example 3 and Comparative Example 1 are shown in the figure. In the XRD pattern, the diffraction peaks at 12.7° and 14.4° represent the unreacted lead iodide and (110) crystal plane of perovskite, respectively. As can be seen from the figure, the diffraction angle of Example 3 does not change significantly, indicating that the hydrazine phenyl phosphite does not change the perovskite structure. The diffraction peak of lead iodide almost does not exist in the perovskite modified by the hydrazine phenyl phosphite additive, indicating that the lead iodide is almost completely converted into perovskite. Compared with Comparative Example 1, the intensity of the diffraction peak corresponding to the (110) crystal plane of Example 3 increases, indicating that the hydrazine phenyl phosphite additive enhances the crystalline quality of the perovskite thin film.

[0102] Figure 6 The UV-Vis graph (left side) and Tauc graph (right side) of Example 3 and Comparative Example 1 are shown in the figure. A slight blue shift phenomenon occurs in Example 3 compared with Comparative Example 1. The band gap of the perovskite thin film obtained from the Tauc graph obtained from the ultraviolet absorption spectrum is also obtained. The band gaps E g of the perovskite layers of Example 3 and Comparative Example 1 are 1.566 eV and 1.564 eV, respectively, and the band gap does not change significantly. This indicates that the hydrazine phenyl phosphite additive does not significantly change the lattice constant of the material, nor does it change the composition ratio of the perovskite layer.

[0103] Figure 7 The SEM graphs of Example 3 and Comparative Example 1 are shown in the figure. The grain size of the perovskite intrinsic layer added with hydrazine phenyl phosphite has a significant increase and is relatively uniform. Compared with Comparative Example 1 without adding hydrazine phenyl phosphite, Example 1 has larger and more uniform grains, which can improve the open-circuit voltage of the device. In addition, from the cross-sectional graph, it can be seen that the perovskite layer of Example 3 added with hydrazine phenyl phosphite and the perovskite layer of Comparative Example 1 without adding the material, the thickness of the perovskite thin film does not change much, both being 680-720 nm, and the grain of the perovskite layer added with hydrazine phenyl phosphite is more processed, indicating that the crystalline quality of the perovskite of Example 3 is better than that of Comparative Example 1.

[0104] Figure 8For the normalized efficiency-time curve of Example 3 and Comparative Example 1, the perovskite solar cell modified with hydrazinobenzenephosphonic acid additive exhibits excellent stability, and after aging in a nitrogen atmosphere for 4800 hours, the device efficiency can still maintain 90.2% of the initial efficiency, which is much better than Comparative Example 1 without hydrazinobenzenephosphonic acid.

[0105] Figure 9 For the lead leakage content chart and device immersion test chart of Example 3 and Comparative Example 1, the lead leakage amount of Example 3 is much smaller than that of Comparative Example 1 after 200 minutes, which proves that the hydrazinobenzenephosphonic acid additive has strong lead fixation ability in the perovskite material, and inhibits the leakage of lead ions in the perovskite.

[0106] Obviously, the above examples of the present application are only examples for clearly illustrating the present application, and are not intended to limit the embodiments of the present application. Based on the above description, other different forms of changes or variations can also be made by those skilled in the art. Here, it is not necessary and also impossible to exhaust all the embodiments. Any modification, equivalent replacement and improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the claims of the present application.

Claims

1. The application of hydrazine-phenylphosphorous acid as an additive in perovskite solar cells; characterized in that, The molecular structure of the hydrazine-phenylphosphine is as follows: ； The chemical formula of the active component in the perovskite precursor solution of the perovskite solar cell is Cs. x (FA) y MA 1-y ) 1- x PbI3, where 0 < x ≤ 0.1, 0.5 ≤ y < 1.

2. The application of hydrazine-phenylphosphorous acid as an additive in the perovskite layer of perovskite solar cells; characterized in that, The molecular structure of the hydrazine-phenylphosphine is as follows: ； The chemical formula of the active component in the perovskite precursor solution of the perovskite solar cell is Cs. x (FA) y MA 1-y ) 1- x PbI3, where 0 < x ≤ 0.1, 0.5 ≤ y < 1.

3. A method for improving the photoelectric efficiency of perovskite solar cells, characterized in that, Hydrazine phosphorous acid is added to the perovskite precursor solution; the molecular structure of hydrazine phosphorous acid is as follows: ； The chemical formula of the active component in the perovskite precursor solution of the perovskite solar cell is Cs. x (FA) y MA 1-y ) 1- x PbI3, where 0 < x ≤ 0.1, 0.5 ≤ y < 1.

4. The method according to claim 3, characterized in that, The concentration of hydrazine-phenylphosphine in the perovskite precursor fluid is 0.1~0.3 mg / mL.

5. A perovskite solar cell, wherein the device structure comprises, from bottom to top, a conductive glass layer, a hole transport layer, a perovskite layer, an electron transport layer, and a metal electrode layer, characterized in that, The perovskite layer contains hydrazine-phenylphosphine; the molecular structure of the hydrazine-phenylphosphine is: ； The chemical formula of the active component in the perovskite precursor solution of the perovskite solar cell is Cs. x (FA) y MA 1-y ) 1- x PbI3, where 0 < x ≤ 0.1, 0.5 ≤ y < 1.

6. The perovskite solar cell according to claim 5, characterized in that, The thickness of the perovskite layer is 680~720nm.

7. A method for preparing a perovskite solar cell as described in claim 5 or 6, comprising: A hole transport layer, a perovskite layer, an electron transport layer, and a metal electrode layer are sequentially prepared on a conductive glass layer using a spin-coating method. The method for preparing the perovskite layer includes the following steps: S1. Hydrazine phosphorous acid is mixed with a perovskite solution to obtain a perovskite precursor solution. S2. Spin-coating the perovskite precursor solution and annealing it by heating to obtain the perovskite layer.

8. The preparation method according to claim 7, characterized in that, The ratio of the total mass of the active components in the perovskite precursor solution to the mass of hydrazine phenylphosphine is (1100~1150): (0.1~0.3).

9. The preparation method according to claim 7, characterized in that, In step S2, the spin coating speed is 3500~4500 rpm.

10. The application of the perovskite solar cell as described in claim 5 or 6 in the fabrication of photovoltaic power generation equipment.

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