A substituted hydrazide-based inorganic perovskite solar cell and its preparation method

Abstract

The present invention discloses an inorganic perovskite solar cell based on substituted hydrazide and a preparation method thereof. The perovskite light absorption layer in the perovskite solar cell contains substituted hydrazide and Pb 2+ The complex is a four-membered ring or five-membered ring structure formed by ‑NH‑NH2, C=O and Pb in the substituted hydrazide, so that Pb is combined in the middle by ‑NH‑NH2 and C=O, and ‑NH‑NH2 and C=O can cooperate with Pb 2+ Forming a strong coordination effect, passivating the uncoordinated Pb in the perovskite 2+ vacancies, forming stable coordination bonds and inhibiting the Pb 0 The terminal NH2 in the substituted hydrazide can also react with I ‑ The formation of hydrogen bonds inhibits the migration of iodide ions in the film. The presence of the complex can reduce the internal defects of the CsPbI3 perovskite film, thereby reducing the non-radiative recombination losses caused by the defects and improving the efficiency and stability of inorganic perovskite cells.

Description

Technical Field

[0001] The present invention belongs to the technical field of perovskite solar cell preparation, and in particular relates to an inorganic perovskite solar cell based on substituted hydrazide and a preparation method thereof. Background Art

[0002] Traditional fossil energy reserves are limited, non-renewable, and their use can cause significant environmental pollution. Therefore, clean, renewable solar energy has become a research hotspot. Among these, solar cells, which directly convert solar energy into electricity, have garnered the most attention. Perovskite solar cells, due to their low cost, low-temperature solution processing, and excellent photoelectric properties (strong broadband light absorption, low exciton binding energy, and long charge carrier transport distance and lifetime), have become thin-film cells with promising commercialization prospects. In just a few years, the efficiency of perovskite solar cells has increased from 3.8% in 2009 to 25.7% today.

[0003] Organic-inorganic hybrid perovskite solar cells have attracted widespread attention from researchers due to their excellent photoelectric performance. However, due to the poor photothermal stability of their A-site organic cations, the stability of this type of cell is poor. In order to solve this problem, Eperon et al. prepared for the first time in 2015 an inorganic CsPbI3 perovskite solar cell with a cell structure of FTO / TiO2 / CsPbI3 / Spiro-OMeTAD / Au and a photoelectric conversion efficiency of 2.9%. This historic breakthrough has become a turning point in the development of photo- and thermally stable inorganic CsPbX3 perovskite solar cells. However, the photoelectric conversion efficiency of inorganic CsPbI3 perovskite solar cells is still low, mainly because of their open circuit voltage loss (V loss The open-circuit voltage of a device is largely determined by the Fermi level difference between the n-type and p-type materials, and is also affected by charge recombination in the device. Summary of the Invention

[0004] The purpose of the present invention is to overcome the shortcomings of the above-mentioned prior art and provide an inorganic perovskite solar cell based on substituted hydrazide and a preparation method thereof, so as to solve the problems of large open-circuit voltage loss of inorganic CsPbI3 perovskite solar cells and internal defects of perovskite films, which cause more non-radiative recombination and thus lead to poor photoelectric performance.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] An inorganic perovskite solar cell based on substituted hydrazide includes a perovskite light-absorbing layer, wherein the perovskite light-absorbing layer is CsPbI3, and the perovskite light-absorbing layer further includes a complex and a substituted hydrazide, wherein the complex is a complex of substituted hydrazide and uncoordinated lead, and the complex is any one of the following structural formulas:

[0007]

[0008] Wherein, X, Y, and Z are alkyl chains, alkoxy chains, or halogens; and X1 is an oxygen group element.

[0009] A further improvement of the present invention is:

[0010] Preferably, the alkyl chain is one of hydrogen, methyl, ethyl, n-propyl, isopropyl, tert-butyl, and dodecyl; the alkoxy chain is one of methoxy, ethoxy, and propoxy; the halogen is one of fluorine, chlorine, and bromine; and the oxygen element is one of oxygen, sulfur, or selenium.

[0011] Preferably, the substituted hydrazide is any one of the following structural formulas:

[0012]

[0013] Preferably, the thickness of the perovskite light-absorbing layer is 350-400 nm.

[0014] A method for preparing an inorganic perovskite solar cell based on substituted hydrazide comprises the following steps:

[0015] A perovskite precursor solution with a concentration of 0.6 to 0.9 M is prepared using hydrogen lead iodine, cesium iodide and substituted hydrazide, wherein the solvent is a mixed solution of DMF and DMSO; wherein the amount of substituted hydrazide added is 1% to 10% of the molar amount of hydrogen lead iodine;

[0016] The substituted hydrazide is any one of the following structural formulas:

[0017]

[0018] The perovskite precursor solution is spin-coated on the electron transport layer, and after annealing, a perovskite light absorbing layer is prepared on the electron transport layer.

[0019] Preferably, the substituted hydrazide is benzohydrazide.

[0020] Preferably, the added amount of the substituted hydrazide is 1.5%, 3% or 6% of the molar amount of hydrogen lead iodine.

[0021] Preferably, the volume ratio of DMF to DMSO in the solvent is 17:3.

[0022] Preferably, the spin coating is divided into two stages. In the first stage, the spin coating speed is 1000 rpm and the spin coating time is 10-15 s; in the second stage, the spin coating speed is 3000-4000 rpm and the spin coating time is 30-40 s.

[0023] Preferably, the annealing temperature is 160-190° C., and the annealing time is 20-80 min.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] The present invention discloses an inorganic perovskite solar cell based on substituted hydrazide and a preparation method thereof. The perovskite light absorption layer in the perovskite solar cell contains substituted hydrazide and Pb 2+ The complex is a complex of -NH-NH2, C=O and Pb in substituted hydrazide 2+ The four-membered ring or five-membered ring structure formed makes Pb 2+ -NH-NH2 and C=O are combined in the middle, and -NH-NH2 and C=O can cooperate with Pb 2+ Forming a strong coordination effect, passivating the uncoordinated Pb in the titanium ore 2+ vacancies, forming stable coordination bonds and inhibiting the Pb 0 The terminal -NH2 in the substituted hydrazide can also react with I - The formation of hydrogen bonds inhibits iodide ion migration within the film. The presence of the complex reduces internal defects in the CsPbI3 perovskite film, thereby reducing non-radiative recombination losses caused by defects and improving the efficiency and stability of the inorganic perovskite solar cell. The addition of substituted hydrazides can elevate the conduction and valence bands of the perovskite film, shifting the Fermi level closer to the conduction band, indicating that the n-type properties of the film are enhanced after the addition of substituted hydrazides. The enhanced n-type perovskite and p-type Spiro-OMeTAD generate an enhanced built-in electric field and a greater driving force for photogenerated carrier separation, improving the energy level matching between the perovskite light absorption layer and the hole transport layer, and reducing the cell's open-circuit voltage loss. Ultimately, the result is an inorganic CsPbI3 perovskite solar cell with a high open-circuit voltage (1.241 V), high photoelectric conversion efficiency (20.47%), and excellent stability (after 1000 hours of storage without encapsulation, the efficiency remains at 98.7% of the initial value).

[0026] Preferably, the substituted hydrazide can be benzoylhydrazide (BH), used as an additive to prepare high-performance inorganic perovskite solar cells. As a small molecule additive with multiple functional groups, BH is cheaper and more readily available than most macromolecular additives, significantly reducing preparation costs. This is also the first application of a hydrazide additive in an inorganic perovskite system.

[0027] In summary, the introduction of substituted hydrazides can effectively reduce the non-radiative recombination and defect state density in the film, and generate a stronger built-in electric field between the perovskite light-absorbing layer and Spiro-OMeTAD, ultimately obtaining inorganic CsPbI3 perovskite solar cells with high open-circuit voltage, excellent photoelectric conversion efficiency and good air stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1Schematic diagram of the structure of the inorganic perovskite solar cell described in Example 1 of the present invention;

[0029] In the figure: 1 is conductive glass; 2 is electron transport layer; 3 is perovskite light absorption layer; 4 is hole transport layer; 5 is metal electrode;

[0030] Figure 2 The thermogravimetric spectrum of BH described in Example 1 of the present invention;

[0031] Figure 3 The BH and Pb described in Example 1 of the present invention 2+ Mass spectrometry of the effect;

[0032] Figure 4 The BH and Pb described in Example 1 of the present invention 2+ XPS spectrum of the effect;

[0033] Figure 5 This is a comparison of XRD patterns of the CsPbI3 perovskite film without BH addition and with BH addition described in Example 1 of the present invention;

[0034] Figure 6 This is a SEM comparison of the CsPbI3 perovskite film without BH addition and with BH addition described in Example 1 of the present invention;

[0035] Among them, (a) is without addition, (b) is with addition;

[0036] Figure 7 Steady-state fluorescence spectra of the CsPbI3 perovskite film without BH addition and with BH addition described in Example 1 of the present invention;

[0037] Figure 8 UPS comparison diagram of the CsPbI3 perovskite film without BH addition and with BH addition described in Example 1 of the present invention;

[0038] Figure 9 JV curves of the CsPbI3 perovskite solar cell without BH addition and with BH addition described in Example 1 of the present invention;

[0039] Figure 10 This is a graphical representation of the air stability of the CsPbI3 perovskite solar cell without BH addition and with BH addition described in Example 1 of the present invention at a humidity of 20-30%. DETAILED DESCRIPTION

[0040] The present invention is further described in detail below with reference to the accompanying drawings and specific embodiments.

[0041] An embodiment of the present invention discloses an inorganic perovskite solar cell, comprising an FTO substrate, an electron transport layer, a perovskite light-absorbing layer, a hole transport layer and a metal electrode stacked in sequence from bottom to top; the perovskite light-absorbing layer comprises CsPbI3, a substituted hydrazide and a complex formed by uncoordinated lead and the substituted hydrazide.

[0042] The substituted hydrazide structure contains -C=O-NH-NH2 and -C=O-NH2 groups, specifically including benzohydrazide (BH), formic hydrazide (FH), benzamide (BA) and p-fluorobenzohydrazide (BHF).

[0043] The general structural formula of the substituted hydrazide is shown as any one of the following:

[0044]

[0045] Pb 2+ The general structure of the complex formed with substituted hydrazide is shown below:

[0046]

[0047] Wherein: X, Y, Z are alkyl chains, alkoxy chains or halogens; X1 is an oxygen group element.

[0048] As one of the preferred embodiments, the alkyl chain is one of hydrogen, methyl, ethyl, n-propyl, isopropyl, tert-butyl, dodecyl, the alkoxy chain is one of methoxy, ethoxy, propoxy, the halogen is one of fluorine, chlorine or bromine; the oxygen element is O, S, Se, etc.

[0049] As one of the preferred embodiments, the thickness of the inorganic perovskite light absorbing layer is 350-400 nm, which is suitable for a perovskite light absorbing layer containing a substituted hydrazide structure, so that the electrical performance of the perovskite light absorbing layer is better.

[0050] As one of the preferred embodiments, the substituted hydrazide is benzoylhydrazide (BH). The structure of BH is to introduce a hydrazine group (-NH-NH2) at one end of the carbonyl group to obtain a hydrazide structure (-C=O-NH-NH2), which can coordinate and passivate Pb 2+ defects; at the same time, the terminal -NH2 group can also react with I - Form hydrogen bonds to increase the 2+ In addition, the other end of the -C=O-NH-NH2 structure in BH is a phenyl structure (electronic conjugation unit). The presence of the phenyl group can reduce the reducibility of the hydrazine group in the material, making the material compatible with Pb 2+ The coordination ability is further improved, and finally a more stable five-membered ring structure is formed.

[0051] The present invention discloses a method for preparing an inorganic perovskite solar cell using a substituted hydrazide, particularly benzoylhydrazide (BH), as an additive, comprising the following steps:

[0052] Step 1, cleaning the conductive glass substrate;

[0053] The conductive glass FTO substrate was cleaned for 30 minutes using a mixture of ultrapure water and glass detergent (v / v=100:1), and then the ultrapure water was changed three times, each for 30 minutes. The cleaned conductive glass FTO substrate was blown dry with an air compressor for later use.

[0054] Step 2, preparing an electron transport layer on a dried and standby conductive glass FTO substrate;

[0055] Preferably, the FTO substrate is treated with UV ozone for 10-15 minutes, and then a layer of TiO2 as an electron transport layer is deposited on the FTO substrate using a TiCl4 aqueous solution by water bath deposition method, the deposition temperature is 70°C, and the deposition time is 60 minutes;

[0056] Preferably, the FTO substrate is treated with ultraviolet ozone for 10-15 minutes, and then SnO2 is prepared as an electron transport layer on the FTO substrate by spin coating using an air compressor.

[0057] Preferably, the prepared electron transport layer is annealed on a hot plate at 200° C. and treated with ultraviolet ozone for 10-15 minutes.

[0058] Step 3, preparing a perovskite precursor solution;

[0059] A CsPbI3 perovskite precursor solution with a concentration of 0.6-0.9 M is prepared using hydrogen lead iodide (HPbI3), cesium iodide (CsI), and benzoylhydrazide (BH). The solvent is a mixed solution of DMF and DMSO in a v / v ratio of 17:3. The substituted hydrazide additive is present at a concentration of 1-10% of the molar amount of HPbI3. The solution is stirred for 12-24 hours before use. This inorganic CsPbI3 perovskite solution containing the substituted hydrazide is used as the perovskite precursor solution.

[0060] As one of the preferred embodiments, the molar amount of the substituted hydrazide in the inorganic perovskite light-absorbing layer is 1% to 10% of the molar amount of HPbI3. Preferably, when the content is 1.5%, 3% or 6%, the defect state density inside the perovskite is low. More preferably, when the molar amount is 3%, the defect state density of the prepared inorganic perovskite film is the lowest and the photoelectric conversion efficiency of the inorganic perovskite solar cell is the best.

[0061] Preferably, the inorganic perovskite precursor solution is prepared in a nitrogen atmosphere glove box to ensure that the perovskite precursor solution is prepared under conditions with low water and oxygen content.

[0062] Step 4, preparing a perovskite light absorbing layer;

[0063] The perovskite precursor solution prepared in step 3 was spin-coated onto the FTO / TiO2 surface in two stages: the first stage at a spin speed of 1000 rpm for 10-15 seconds; the second stage at a spin speed of 3000-4000 rpm for 30-40 seconds. After spin coating, the solution was annealed at a temperature of 160-190°C for 20-80 minutes to produce a FTO / TiO2 / CsPbI3 perovskite light-absorbing layer with a thickness of approximately 350-400 nm.

[0064] Step 5, preparing a hole transport layer;

[0065] Spiro-OMeTAD was used as the hole transport layer. 90 mg of Spiro-OMeTAD was dissolved in 1 mL of chlorobenzene, and then 22 μL of Li + salt and 36 μL of tBP to prepare a hole transport layer precursor solution.

[0066] The CsPbI3 perovskite light-absorbing layer prepared in step 4 was spin-coated at 2000-3000 rpm for 0 s and 5000 rpm for 30 s to obtain a FTO / TiO2 / CsPbI3 / Spiro-OMeTAD structure.

[0067] Step 6: Vapor-deposit a 60-80 nm gold electrode on the hole transport layer prepared in step 5, and finally obtain an inorganic CsPbI3 perovskite solar cell with a device structure of FTO / TiO2 / CsPbI3 / Spiro-OMeTAD / Au.

[0068] like Figure 1 As shown, the structure of the inorganic CsPbI3 perovskite solar cell prepared by the above method is, from bottom to top, a conductive glass 1, an electron transport layer 2, a BH-added perovskite light-absorbing layer 3, a hole transport layer 4 and a metal electrode 5.

[0069] The following is a further description of the specific embodiments.

[0070] Example 1

[0071] First, clean the conductive glass substrate: use a mixture of ultrapure water and glass detergent v / v = 100:1 to clean the conductive glass FTO substrate for 30 minutes, then change the ultrapure water three times, each cleaning for 30 minutes, and use an air compressor to blow dry the cleaned conductive glass FTO substrate for later use.

[0072] Second, an electron transport layer was prepared on a blow-dried, standby conductive glass FTO substrate: the FTO substrate was treated with UV ozone for 10-15 minutes, and then a layer of TiO2 as an electron transport layer was deposited on the FTO substrate using a TiCl4 aqueous solution using a water bath deposition method. The deposition temperature was 70°C and the deposition time was 60 minutes.

[0073] Third, prepare a perovskite precursor solution: Prepare a 0.745M CsPbI3 perovskite precursor solution. Dissolve 0.4387g HPbI3 and 0.1935g CsI in a 17:3 volume ratio of DMF to DMSO to create a 0.745M inorganic CsPbI3 perovskite precursor solution. Add BH to the precursor solution at a concentration of 3% of the molar ratio of hydrogen, lead, and iodine. Stir the solution for 24 hours before use.

[0074] Fourth, prepare the perovskite light-absorbing layer: The perovskite precursor solution prepared in step 3 was spin-coated onto the FTO / TiO2 surface in two stages: the first stage at a speed of 1000 rpm for 10 seconds; the second stage at 3000 rpm for 40 seconds. After spin-coating, the solution was annealed at 160°C for 80 minutes, resulting in a FTO / TiO2 / CsPbI3-BH perovskite light-absorbing layer with a thickness of approximately 380 nm.

[0075] Fifth, prepare the hole transport layer: Spiro-OMeTAD was used as the hole transport layer. 90 mg of Spiro-OMeTAD was dissolved in 1 mL of chlorobenzene, followed by the addition of 22 μL of lithium salt and 36 μL of tBP. The layer was spin-coated onto the CsPbI3 perovskite absorber prepared in step 4 using a process of 3000 rpm for 0 s and 5000 rpm for 30 s, resulting in a FTO / TiO2 / CsPbI3-BH / Spiro-OMeTAD structure.

[0076] Sixth, an 80nm gold electrode was evaporated on the hole transport layer prepared in step 5, and the inorganic CsPbI3 perovskite solar cell with a device structure of FTO / TiO2 / CsPbI3-BH / Spiro-OMeTAD / Au was finally obtained. The effective active area of ​​the cell was 0.09cm 2 .

[0077] In this example, a 3% BH-doped inorganic CsPbI3 perovskite solar cell was prepared.

[0078] Figure 1Figure 1 shows the structure of an inorganic CsPbI3 perovskite solar cell. In the figure, 1 is the conductive glass, 2 is the electron transport layer, 3 is the perovskite light-absorbing layer with substituted hydrazide BH added, 4 is the hole transport layer, and 5 is the metal electrode. The added BH content is 3%, the electron transport material is TiO2, and the hole transport material is Spiro-OMeTAD.

[0079] Figure 2 The figure shows the thermogravimetric spectrum of substituted hydrazide (BH). It can be seen from the figure that the thermal decomposition temperature of BH is 190°C, indicating that there is no decomposition process during the annealing process of the perovskite film.

[0080] Figure 3 As shown, BH and Pb in perovskite 2+ There is a strong bonding interaction, as evidenced by the molecular weight of 343.990 in the figure.

[0081] Figure 4 Shown are BH and Pb 2+ The XPS spectrum of the interaction between the N and O elements in BH and the Pb element in the perovskite shows a large shift toward the direction of high binding energy, which indicates that the multifunctional groups in BH and Pb 2+ There is a strong interaction.

[0082] like Figure 5 As shown in the figure, the CsPbI3 perovskite film with the addition of BH has better crystallinity than the perovskite film without BH, and the peak intensity is significantly enhanced, indicating that the addition of BH improves the crystallization quality of the perovskite film.

[0083] like Figure 6 As shown in the figure, after adding BH, the CsPbI3 perovskite film is denser, the surface of the film has no obvious holes, and is smoother.

[0084] from Figure 7 It can be seen that the CsPbI3 perovskite film after adding BH has a higher steady-state fluorescence peak than the perovskite film without BH, which further proves that the crystallinity of the film improves and the non-radiative recombination is reduced after the addition of BH.

[0085] Depend on Figure 8 It can be seen that the addition of BH can improve the conduction band and valence band of the CsPbI3 perovskite film, while enhancing the built-in electric field between the perovskite film and Spiro-OMeTAD, thereby effectively improving the open circuit voltage of the device.

[0086] like Figure 9 As shown in the figure, after adding BH, the open circuit voltage of the CsPbI3 perovskite solar cell was greatly improved to 1.241V, and the prepared device achieved a photoelectric conversion efficiency of 20.47%.

[0087] Depend on Figure 10 It can be seen that the unpackaged device with BH added can still maintain 98.4% of its initial efficiency after 1000 hours in an environment with an air humidity of 20%-30%, while the efficiency of the device without BH added is only 82.4% of its initial efficiency.

[0088] Comparative Example

[0089] All steps and parameters of the comparative example are the same as those of Example 1, except that BH is not added when preparing the perovskite precursor solution in step 3. The device structure of the finally prepared CsPbI3 perovskite solar cell is FTO / TiO2 / CsPbI3 / Spiro-OMeTAD / Au.

[0090] Figure 1 Figure 1 shows the structure of an inorganic CsPbI3 perovskite solar cell. In the figure, 1 is conductive glass, 2 is the electron transport layer, 3 is the traditional perovskite light-absorbing layer, 4 is the hole transport layer, and 5 is the metal electrode. The electron transport material is TiO2, and the hole transport material is Spiro-OMeTAD.

[0091] Figure 5 Shown in the figure are the XRD spectra of CsPbI3 perovskite films without and with the addition of BH. It can be seen from the figure that the film with the addition of BH has better crystallinity.

[0092] Figure 6 (a) and (b) are SEM images of CsPbI3 perovskite films without and with BH added. Comparing (a) and (b), we can see that the film without BH has more pores on its surface, while the film with BH has no obvious pores and is smoother.

[0093] Figure 8 This is a UPS comparison diagram of the perovskite film with BH added in Example 1 and the perovskite film without BH added in the comparative example. From the figure, we can see the conduction band and valence band of the CsPbI3 perovskite film without BH added, and at the same time, the built-in electric field between the perovskite film and Spiro-OMeTAD is enhanced.

[0094] like Figure 9 As shown, the photoelectric conversion efficiency of the inorganic CsPbI3 perovskite device with BH added in Example 1 was compared with that of the comparative example without BH added. The specific parameters are shown in Table 1. Compared with the device without BH added, the open circuit voltage of the device after BH addition increased from 1.166V to 1.241V, an increase of 75mV, and the corresponding photoelectric conversion efficiency of the device also increased from the initial 18.57% to 20.47%.

[0095] Figure 10The figure shows a comparison of the air stability of the device in Example 1 and the device in the comparative example in an environment with an air humidity of 20%-30%. The figure has been normalized. As can be seen from the figure, the air stability of the device with BH added is significantly better than that of the device without BH, indicating that BH can also significantly improve the air stability of the device.

[0096] Table 1

[0097]

[0098] Example 2

[0099] In this example, the prepared CsPbI3 perovskite precursor solution contained 1.5% BH. The remaining steps were the same as in Example 1. In this example, the perovskite cell device with 1.5% BH addition had an open circuit voltage of 1.200 V and a photoelectric conversion efficiency of 19.68%.

[0100] Example 3

[0101] In this example, the prepared CsPbI3 perovskite precursor solution contained 6% BH. The remaining steps were the same as in Example 1. In this example, the perovskite cell device with 6% BH addition had an open circuit voltage of 1.196 V and a photoelectric conversion efficiency of 19.30%.

[0102] Example 4

[0103] In this example, a CsPbI3 perovskite precursor solution was prepared with formic hydrazide (FH) as an additive. When the FH content was 3%, the perovskite solar cell device achieved an open circuit voltage of 1.199 V and a photoelectric conversion efficiency of 19.24%. Parameters not discussed in this example were the same as those in Example 1.

[0104] Example 5

[0105] In this example, a CsPbI3 perovskite precursor solution was prepared with benzamide (BA) as an additive. When the BA content was 3%, the perovskite solar cell device achieved an open circuit voltage of 1.172V and a photoelectric conversion efficiency of 19.05%. Parameters not discussed in this example were the same as those in Example 1.

[0106] Example 6

[0107] In this example, a CsPbI3 perovskite precursor solution was prepared with a para-fluorinated hydrazide (BHF) additive. When the BHF content was 3%, the perovskite solar cell device achieved an open circuit voltage of 1.205V and a photoelectric conversion efficiency of 19.97%. Parameters not discussed in this example were the same as those in Example 1.

[0108] Example 7

[0109] In this embodiment, the electron transport layer is SnO2, and the method for preparing the electron transport layer is spin coating. Parameters not mentioned in this embodiment are the same as those in Example 1.

[0110] Example 8

[0111] In this embodiment, when spin-coating the inorganic perovskite light absorbing layer, the first stage of the spin coating process is: 15s, 1000rpm,; the second stage of the spin coating process is: 3000rpm, 40s. The parameters not mentioned in this embodiment are the same as those in Example 1.

[0112] Example 9

[0113] In this embodiment, when the inorganic perovskite light absorbing layer is spin-coated, the first stage of the spin coating process is: 10s, 1000rpm; the second stage of the spin coating process is: 40s, 4000rpm. The parameters not mentioned in this embodiment are the same as those in Example 1.

[0114] Example 10

[0115] In this embodiment, when the inorganic perovskite light absorbing layer is spin-coated, the first stage of the spin coating process is: 13s, 1000rpm; the second stage of the spin coating process is: 35s, 3500rpm. The parameters not mentioned in this embodiment are the same as those in Example 1.

[0116] Example 11 In this example, the thickness of the inorganic perovskite light absorbing layer is 350 nm. Parameters not mentioned in this example are the same as those in Example 1.

[0117] Example 12

[0118] In this embodiment, the thickness of the inorganic perovskite light absorbing layer is 400 nm. Parameters not mentioned in this embodiment are the same as those in Example 1.

[0119] Example 13

[0120] In this embodiment, the spin-coated inorganic perovskite light-absorbing layer was annealed at a temperature of 170° C. for 55 minutes. Parameters not mentioned in this embodiment are the same as those in Example 1.

[0121] Example 14

[0122] In this embodiment, the spin-coated inorganic perovskite light-absorbing layer was annealed at a temperature of 180° C. for 35 minutes. Parameters not mentioned in this embodiment are the same as those in Example 1.

[0123] Example 15

[0124] In this embodiment, the spin-coated inorganic perovskite light-absorbing layer was annealed at a temperature of 190° C. for 20 minutes. Parameters not mentioned in this embodiment are the same as those in Example 1.

[0125] Example 16

[0126] In this embodiment, when the hole transport layer is spin-coated, the first stage of the spin coating process is: 0s, 2000rpm; the second stage of the spin coating process is: 30s, 5000rpm. Parameters not mentioned in this embodiment are the same as those in Example 1.

[0127] Example 17

[0128] In this embodiment, when the hole transport layer is spin-coated, the first stage of the spin coating process is: 0s, 2500rpm; the second stage of the spin coating process is: 30s, 5000rpm. Parameters not mentioned in this embodiment are the same as those in Example 1.

[0129] Example 18

[0130] In this embodiment, the counter electrode is a gold electrode with an evaporation thickness of 60 nm. Parameters not mentioned in this embodiment are the same as those in Example 1.

[0131] Example 19

[0132] In this embodiment, the counter electrode is a gold electrode with an evaporation thickness of 70 nm. Parameters not mentioned in this embodiment are the same as those in Example 1.

[0133] Example 20

[0134] In this embodiment, the molar amount of the substituted hydrazide is 1% of the molar amount of HPbI3, and the structural formula of the substituted hydrazide is as follows:

[0135]

[0136] The structural formula of the complex in the generated light-absorbing layer is:

[0137]

[0138] wherein X, Y and Z are all methyl groups.

[0139] The parts not involved in this embodiment are the same as those in Example 1.

[0140] Example 21

[0141] In this embodiment, the molar amount of the substituted hydrazide is 10% of the molar amount of HPbI3, and the structural formula of the substituted hydrazide is as follows:

[0142]

[0143] The structural formula of the complex in the generated light-absorbing layer is:

[0144]

[0145] Wherein, X, Y, and Z are all ethyl groups.

[0146] The parts not involved in this embodiment are the same as those in Example 1.

[0147] The parts not involved in this embodiment are the same as those in Example 1.

[0148] Example 22

[0149] In this embodiment, the molar amount of the substituted hydrazide is 8% of the molar amount of HPbI3, and the structural formula of the substituted hydrazide is as follows:

[0150]

[0151] The structural formula of the complex in the generated light-absorbing layer is:

[0152]

[0153] Wherein, X and Y are hydrogen, and Z is isopropyl;

[0154] The parts not involved in this embodiment are the same as those in Example 1.

[0155] Example 23

[0156] In this embodiment, the molar amount of the substituted hydrazide is 4% of the molar amount of HPbI3, and the structural formula of the substituted hydrazide is as follows:

[0157]

[0158] The structural formula of the complex in the generated light-absorbing layer is:

[0159]

[0160] Wherein, X and Y are hydrogen, and Z is n-propyl;

[0161] Example 24

[0162] In this embodiment, the molar amount of the substituted hydrazide is 5% of the molar amount of HPbI3, and the structural formula of the substituted hydrazide is as follows:

[0163]

[0164] The structural formula of the complex in the generated light-absorbing layer is:

[0165]

[0166] Wherein, X and Z are hydrogen, and Y is tert-butyl;

[0167] The parts not involved in this embodiment are the same as those in Example 1.

[0168] Example 25

[0169] In this embodiment, the molar amount of the substituted hydrazide is 3% of the molar amount of HPbI3, and the structural formula of the substituted hydrazide is as follows:

[0170]

[0171] The structural formula of the complex in the generated light-absorbing layer is:

[0172]

[0173] Wherein, X and Y are methyl groups, and Z is dodecyl group;

[0174] The parts not involved in this embodiment are the same as those in Example 1.

[0175] Example 26

[0176] In this embodiment, the molar amount of the substituted hydrazide is 2% of the molar amount of HPbI3, and the structural formula of the substituted hydrazide is as follows:

[0177]

[0178] The structural formula of the complex in the generated light-absorbing layer is:

[0179]

[0180] wherein X, Y and Z are all methoxy;

[0181] The parts not involved in this embodiment are the same as those in Example 1.

[0182] Example 27

[0183] In this embodiment, the molar amount of the substituted hydrazide is 4% of the molar amount of HPbI3, and the structural formula of the substituted hydrazide is as follows:

[0184]

[0185] The structural formula of the complex in the generated light-absorbing layer is:

[0186]

[0187] Wherein, X and Y are hydrogen, and Z is ethoxy;

[0188] The parts not involved in this embodiment are the same as those in Example 1.

[0189] Example 28

[0190] In this embodiment, the molar amount of the substituted hydrazide is 3% of the molar amount of HPbI3, and the structural formula of the substituted hydrazide is as follows:

[0191]

[0192] The structural formula of the complex in the generated light-absorbing layer is:

[0193]

[0194] wherein X is hydrogen, Y and Z are propoxy;

[0195] The parts not involved in this embodiment are the same as those in Example 1.

[0196] Example 29

[0197] In this embodiment, the molar amount of the substituted hydrazide is 6% of the molar amount of HPbI3, and the structural formula of the substituted hydrazide is as follows:

[0198]

[0199] The structural formula of the complex in the generated light-absorbing layer is:

[0200]

[0201] wherein X, Y and Z are all fluorine;

[0202] The parts not involved in this embodiment are the same as those in Example 1.

[0203] Example 30

[0204] In this embodiment, the molar amount of the substituted hydrazide is 1.5% of the molar amount of HPbI3, and the structural formula of the substituted hydrazide is as follows:

[0205]

[0206] The structural formula of the complex in the generated light-absorbing layer is:

[0207]

[0208] wherein X, Y and Z are all chlorine;

[0209] The parts not involved in this embodiment are the same as those in Example 1.

[0210] Example 31

[0211] In this embodiment, the molar amount of the substituted hydrazide is 6% of the molar amount of HPbI3, and the structural formula of the substituted hydrazide is as follows:

[0212]

[0213] The structural formula of the complex in the generated light-absorbing layer is:

[0214]

[0215] Wherein, X is a methyl group.

[0216] The parts not involved in this embodiment are the same as those in Example 1.

[0217] Example 32

[0218] In this embodiment, the molar amount of the substituted hydrazide is 6% of the molar amount of HPbI3, and the structural formula of the substituted hydrazide is as follows:

[0219]

[0220] The structural formula of the complex in the generated light-absorbing layer is:

[0221]

[0222] Among them, X1 is oxygen

[0223] The parts not involved in this embodiment are the same as those in Example 1.

[0224] Example 33

[0225] In this embodiment, the molar amount of the substituted hydrazide is 3% of the molar amount of HPbI3, and the structural formula of the substituted hydrazide is as follows:

[0226]

[0227] The structural formula of the complex in the generated light-absorbing layer is:

[0228]

[0229] Wherein, X1 is sulfur;

[0230] The parts not involved in this embodiment are the same as those in Example 1.

[0231] Example 34

[0232] In this embodiment, the molar amount of the substituted hydrazide is 3% of the molar amount of HPbI3, and the structural formula of the substituted hydrazide is as follows:

[0233]

[0234] The structural formula of the complex in the generated light-absorbing layer is:

[0235]

[0236] Wherein, X1 is selenium;

[0237] The parts not involved in this embodiment are the same as those in Example 1.

[0238] Example 35

[0239] In this embodiment, the molar amount of the substituted hydrazide is 3% of the molar amount of HPbI3, and the structural formula of the substituted hydrazide is as follows:

[0240]

[0241] The structural formula of the complex in the generated light-absorbing layer is:

[0242]

[0243] Wherein, X is oxygen;

[0244] The parts not involved in this embodiment are the same as those in Example 1.

[0245] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing an inorganic perovskite solar cell based on substituted hydrazide, characterized in that: The following steps are involved: A perovskite precursor solution with a concentration of 0.6-0.9 M is prepared using hydrogen lead iodine, cesium iodide and substituted hydrazide, wherein the solvent is a mixed solution of DMF and DMSO; wherein the amount of substituted hydrazide added is 1%-10% of the molar amount of hydrogen lead iodine; The substituted hydrazide is any one of the following structural formulas: Wherein, X, Y, and Z are alkyl chains, alkoxy chains, or halogens; X1 is an oxygen element; The perovskite precursor solution is spin-coated on the electron transport layer, and after annealing, a perovskite light absorbing layer is prepared on the electron transport layer.

2. The method for preparing an inorganic perovskite solar cell based on substituted hydrazide according to claim 1, wherein The substituted hydrazide is benzoylhydrazide.

3. The method for preparing an inorganic perovskite solar cell based on substituted hydrazide according to claim 1, wherein: The added amount of the substituted hydrazide is 1.5%, 3% or 6% of the molar amount of hydrogen lead iodine.

4. The method for preparing an inorganic perovskite solar cell based on substituted hydrazide according to claim 1, wherein: The volume ratio of DMF to DMSO in the solvent is 17:

3.

5. The method for preparing an inorganic perovskite solar cell based on substituted hydrazide according to claim 1, wherein: Spin coating is divided into two stages. In the first stage, the spin coating speed is 1000 rpm and the spin coating time is 10-15 s; in the second stage, the spin coating speed is 3000-4000 rpm and the spin coating time is 30-40 s.

6. The method for preparing an inorganic perovskite solar cell based on substituted hydrazide according to any one of claims 1 to 5, characterized in that: Annealing temperature is 160-190 o C, annealing time is 20-80 min.

7. An inorganic perovskite solar cell based on substituted hydrazide prepared by the preparation method according to claim 1, characterized in that: The invention comprises a perovskite light-absorbing layer, wherein the perovskite light-absorbing layer is CsPbI3, and the perovskite light-absorbing layer further comprises a complex and a substituted hydrazide, wherein the complex is a complex of a substituted hydrazide and uncoordinated lead, and the complex is any one of the following structural formulas: Wherein, X, Y, and Z are alkyl chains, alkoxy chains, or halogens; and X1 is an oxygen group element.

8. The inorganic perovskite solar cell based on substituted hydrazide according to claim 7, characterized in that: The alkyl chain is one of methyl, ethyl, n-propyl, isopropyl, tert-butyl, and dodecyl; the alkoxy chain is one of methoxy, ethoxy, and propoxy; the halogen is one of fluorine, chlorine, and bromine; and the oxygen element is one of oxygen, sulfur, or selenium.

9. The inorganic perovskite solar cell based on substituted hydrazide according to claim 7, characterized in that: The thickness of the perovskite light-absorbing layer is 350-400 nm.

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