Perovskite precursor solution, preparation method thereof and perovskite photovoltaic cell

Abstract

The invention relates to a perovskite precursor solution, a preparation method thereof and a perovskite photovoltaic cell. The perovskite precursor solution contains perovskite, a solvent and an additive, the additive contains a corrosion inhibitor; the dosage ratio of the perovskite to the additive in the perovskite precursor solution is (1-10) mol: (0.5-25) g. In the invention, the corrosion inhibitor is used as an additive, so that the prepared perovskite precursor solution can be stored or transported in the air for a long time, and the longest time can reach 40-60 days. Compared with a photovoltaic cell prepared from a freshly prepared precursor solution, a perovskite photovoltaic cell prepared after the perovskite precursor solution is stored for a long time has consistent or better photoelectric properties. According to the perovskite precursor solution, the manufacturing cost of a perovskite photovoltaic device can be reduced, and the perovskite precursor solution becomes a commodity which can be circulated.

Description

Technical Field

[0001] The present invention relates to the technical field of photovoltaic cells, and particularly to a perovskite precursor solution, a preparation method thereof, and a perovskite photovoltaic cell. Background Art

[0002] Currently, the preparation of perovskite photovoltaic devices in air has become a mainstream trend. However, perovskite precursor solutions cannot be stored in air for a long time, which has become a limiting factor for cost reduction and an important reason why perovskite precursor solutions cannot be circulated as independent products.

[0003] Therefore, there is an urgent need to develop a method that enables perovskite precursor solutions to be stored in air for a long time. Summary of the Invention

[0004] Based on this, in view of the problem that existing perovskite precursor solutions cannot be stored in air for a long time, it is necessary to provide a perovskite precursor solution, a preparation method thereof, and a perovskite photovoltaic cell.

[0005] A perovskite precursor solution contains perovskite, a solvent, and an additive; the additive contains a corrosion inhibitor; the dosage ratio of the perovskite to the additive in the perovskite precursor solution is (1-10) mol:(0.5-25) g.

[0006] In the above perovskite precursor solution, the corrosion inhibitor is used as an additive, so that the prepared perovskite precursor solution can be stored or transported in air for a long time, up to 40-60 days at most. The perovskite photovoltaic cell prepared from the perovskite precursor solution after long-term storage has the same or better optoelectronic performance as the photovoltaic cell prepared from the freshly prepared precursor solution. This perovskite precursor solution can not only reduce the manufacturing cost of perovskite photovoltaic devices, but also make the perovskite precursor solution a commodity that can be circulated.

[0007] In one embodiment, the concentration of the perovskite is 0.2 M - 2 M.

[0008] In one embodiment, the corrosion inhibitor includes at least one of organic phosphorus-based corrosion inhibitors, phosphono-carboxylic acid copolymer-based corrosion inhibitors, and metal-specific corrosion inhibitors.

[0009] In one embodiment, the organophosphorus corrosion inhibitor includes at least one of amino trimethylene phosphonic acid (ATMP), hydroxyethylidene diphosphonic acid (HEDP), diethylenetriamine pentamethylene phosphonic acid (DTPMPA), ethylene diamine tetramethylene phosphonic acid (EDTMPS), 2-hydroxyphosphonoacetic acid (HPAA); the phosphonyl carboxylic acid copolymer corrosion inhibitor includes at least one of polyepoxysuccinic acid (PESA), polyaspartic acid (PASP); the metal-specific corrosion inhibitor includes at least one of methylene bisthiocyanate (MBT), benzotriazole (BTA), methylbenzotriazole (TTA).

[0010] In one embodiment, the structure of the perovskite is ABX3, where A is a monovalent cation, B is a divalent cation, and X is a monovalent anion; A includes at least one of methylamine, formamidine, cesium, rubidium, PEA + , PMA + , OA + ; B includes at least one of lead, tin, antimony, gallium or strontium, and X includes at least one of fluorine, iodine, bromine, chlorine, BF4 - , BF3 - .

[0011] In one embodiment, the solvent includes at least one of DMF, DMSO, NMP, 2-Me, DMPU, CHP, DPSO, DMI, THF, TMS, PC, MeCN, EC, DMAC, NBP, NFM, CHP, TMSO, GBL, 2Me-THF, TBPp, HBD-HBA, Cyrene.

[0012] The present invention also provides a method for preparing the perovskite precursor solution, including the following steps: calculating the dosages of each raw material, weighing the raw materials according to the ratio, and dissolving them in the solvent to obtain the solution.

[0013] The present invention also provides a perovskite photovoltaic cell, including a perovskite light-absorbing layer, and the perovskite light-absorbing layer includes a perovskite thin film, and the perovskite thin film is prepared from the perovskite precursor solution described in any one of the above.

[0014] In one embodiment, the method for preparing the perovskite thin film includes, but is not limited to, spin coating, blade coating, spraying, slot-die coating, R2R coating.

[0015] In one embodiment, the perovskite photovoltaic cell includes a first electrode layer, a first charge transport layer, a perovskite light-absorbing layer, a second charge transport layer, and a second electrode layer that are sequentially stacked from bottom to top.

[0016] In one embodiment, the first electrode layer is a transparent conductive layer, and the transparent conductive layer contains at least one of indium tin oxide (ITO), indium tin oxide doped with tungsten (IWO), zinc oxide doped with aluminum (AZO), tin oxide doped with fluorine (FTO), tin oxide doped with antimony (ATO), zinc oxide doped with gallium (GZO), titanium oxide (TiO2) based doped with metal elements; the first charge transport layer is a hole transport layer, and the hole transport layer contains at least one of Spiro-OMeTAD, CuSCN, NiOx, PTAA, SAM, polymerized SAM, Me-4PACz, small molecule organic hole transport layer; the second charge transport layer is an electron transport layer, and the electron transport layer contains C 60 ; the second electrode layer contains at least one of Au, Ag, Cu, Cr, Ni, Mo, W, Pt, Pd, V, ITO, IWO, FTO, AZO, GZO.

[0017] The present invention also provides a preparation method of the perovskite photovoltaic cell as described above, including the following steps: preparing a perovskite light-absorbing layer; the specific method for preparing the perovskite light-absorbing layer is: depositing and forming a film from the perovskite precursor solution as described in any one of the above, and annealing to obtain.

[0018] In one embodiment, the preparation method of the perovskite photovoltaic cell as described above includes the following steps: preparing a first charge transport layer; preparing a perovskite light-absorbing layer; preparing a second charge transport layer; preparing a second electrode layer.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] For the perovskite precursor solution, its preparation method, and the perovskite photovoltaic cell of the present invention, by using a corrosion inhibitor as an additive, the prepared perovskite precursor solution can be stored or transported in air for a long time, up to 40 to 60 days at most. The perovskite photovoltaic cell prepared from the perovskite precursor solution after long-term storage has the same or better optoelectronic performance compared with the photovoltaic cell prepared from the freshly prepared precursor solution. The perovskite precursor solution not only can reduce the manufacturing cost of perovskite photovoltaic devices, but also makes the perovskite precursor solution become a commodity that can be circulated. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 It is the XRD pattern of the perovskite thin film corresponding to Example 1 in Experimental Example 1;

[0022] Figure 2 It is the XRD pattern of the perovskite thin film corresponding to Comparative Example 1 in Experimental Example 1;

[0023] Figure 3 It is the XRD pattern of the perovskite thin film corresponding to Example 2 in Experimental Example 1;

[0024] Figure 4 XRD pattern of the perovskite thin film corresponding to Comparative Example 2 in Experimental Example 1;

[0025] Figure 5 XRD pattern of the perovskite thin film corresponding to Example 3 in Experimental Example 1;

[0026] Figure 6 XRD pattern of the perovskite thin film corresponding to Comparative Example 3 in Experimental Example 1;

[0027] Figure 7 XRD pattern of the perovskite thin film corresponding to Example 4 in Experimental Example 1;

[0028] Figure 8 XRD pattern of the perovskite thin film corresponding to Example 5 in Experimental Example 1;

[0029] Figure 9 Appearance comparison diagram of the perovskite thin films corresponding to Example 1 and Comparative Example 1 in Experimental Example 1;

[0030] Figure 10 Appearance comparison diagram of the perovskite thin films corresponding to Example 2 and Comparative Example 2 in Experimental Example 1;

[0031] Figure 11 Appearance comparison diagram of the perovskite thin films corresponding to Example 3 and Comparative Example 3 in Experimental Example 1;

[0032] Figure 12 I-V characteristic diagram of the perovskite photovoltaic module corresponding to Example 1 in Experimental Example 2;

[0033] Figure 13 I-V characteristic diagram of the perovskite photovoltaic module corresponding to Comparative Example 1 in Experimental Example 2;

[0034] Figure 14 I-V characteristic diagram of the perovskite photovoltaic module corresponding to Example 2 in Experimental Example 2;

[0035] Figure 15 I-V characteristic diagram of the perovskite photovoltaic module corresponding to Comparative Example 2 in Experimental Example 2;

[0036] Figure 16 I-V characteristic diagram of the perovskite photovoltaic module corresponding to Example 3 in Experimental Example 2;

[0037] Figure 17 I-V characteristic diagram of the perovskite photovoltaic module corresponding to Comparative Example 3 in Experimental Example 2;

[0038] Figure 18 I-V characteristic diagram of the perovskite photovoltaic module corresponding to Example 4 in Experimental Example 2;

[0039] Figure 19 It is the I-V characteristic diagram of the perovskite photovoltaic module corresponding to Example 5 in Experimental Example 2;

[0040] Figure 20 It is the appearance comparison of the aging situation of the perovskite precursor solution in Example 1 and Comparative Example 1 in Experimental Example 3;

[0041] Figure 21 It is the PL spectrogram of the perovskite thin film corresponding to Example 1 in Experimental Example 3;

[0042] Figure 22 It is the PL spectrogram of the perovskite thin film corresponding to Comparative Example 1 in Experimental Example 3;

[0043] Figure 23 It is the comparison diagram of the I-V characteristic curves of the perovskite photovoltaic cells prepared in Example 6 and Comparative Example 4 in Experimental Example 3. The detection result corresponding to Example 6 is marked as W, and the detection result corresponding to Comparative Example 4 is marked as WO;

[0044] Figure 24 It is the statistical result of the relationship between the electrical performance parameters of the perovskite photovoltaic cell corresponding to Example 1 in Experimental Example 3 and the solution storage time;

[0045] Figure 25 It is the statistical result of the relationship between the electrical performance parameters of the perovskite photovoltaic cell corresponding to Comparative Example 1 in Experimental Example 3 and the solution storage time;

[0046] Figure 26 It is the comparison diagram of the photoelectric conversion efficiency of the perovskite photovoltaic cells corresponding to Example 1 and Comparative Example 1 in Experimental Example 3 changing with the solution storage time. The detection result corresponding to Example 1 is marked as W, and the detection result corresponding to Comparative Example 1 is marked as WO;

[0047] Figure 27 It is the comparison diagram of the damp heat aging detection results of the perovskite photovoltaic cells in Example 6 and Comparative Example 4 in Experimental Example 3. The detection result corresponding to Example 1 is marked as W, and the detection result corresponding to Comparative Example 1 is marked as WO;

[0048] Figure 28 It is the comparison diagram of the statistical results of the photoelectric conversion efficiency of the perovskite photovoltaic cells corresponding to Example 1 and Comparative Example 1 in Experimental Example 3. The detection result corresponding to Example 1 is marked as W, and the detection result corresponding to Comparative Example 1 is marked as WO;

[0049] Figure 29 It is the comparison diagram of the statistical results of the photoelectric conversion efficiency of the perovskite photovoltaic cells corresponding to Example 1 and Comparative Example 1 in Experimental Example 3. The detection result corresponding to Example 1 is marked as W, and the detection result corresponding to Comparative Example 1 is marked as WO. DETAILED DESCRIPTION

[0050] In order to facilitate the understanding of the present invention, the present invention will be described more fully below with reference to the relevant drawings. The preferred embodiments of the present invention are given in the drawings. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0051] It should be noted that when an element is referred to as being "fixed to" another element, it may be directly on the other element or there may be an intermediate element. When an element is considered to be "connected to" another element, it may be directly connected to the other element or there may be an intermediate element at the same time.

[0052] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which the present invention belongs. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.

[0053] The reagents used in the following examples, unless otherwise specified, are all commercially available; the methods used in the following examples, unless otherwise specified, are all achievable by conventional methods; in the following examples, unless otherwise specified, the conditions for preparing the solutions are all at room temperature and pressure, and the effects of the added solutes on the solution volume are all negligible.

[0054] Example 1

[0055] A perovskite precursor solution contains perovskite, a solvent and an additive; the additive is ATMP (aminotrimethylene phosphoric acid, solid, CAS: 6419-19-8, purchased from Aladdin); the concentration of perovskite in the perovskite precursor solution is 1.5M, and the structural formula of perovskite is (CsPbI3) 0.02 (FAPbI3) 0.98 The dosage ratio of perovskite to additive is 1.5 mol:5 g, and the solvent is a DMF / DMSO mixture with a volume ratio of 4:1.

[0056] The preparation method of the above-mentioned perovskite precursor solution has the following specific steps: according to the structural formula of perovskite and the above-mentioned numerical values ​​and ratios, the amount of each raw material is calculated; cesium iodide (CsI), formamidine hydroiodide (FAI), lead iodide (PbI2), and methylamine chloride (MACl) are weighed and dissolved in a solvent (DMF / DMSO mixed solution with a volume ratio of 4:1), so that the concentration of cesium iodide (CsI) in the solution is 0.03M, the concentration of formamidine hydroiodide (FAI) is 1.5M, the concentration of lead iodide (PbI2) is 1.5M, and the concentration of methylamine chloride (MACl) is 0.3M, and the solution is cooled, shaken or stirred to dissolve until clear to obtain a solution; take 1mL of solution a, weigh 5mg of ATMP, and dissolve it in 1mL of solution a to obtain a perovskite precursor solution.

[0057] Example 2

[0058] A perovskite precursor solution contains perovskite, a solvent and an additive; the additive is ATMP (aminotrimethylene phosphoric acid, solid, CAS: 6419-19-8, purchased from Aladdin); the concentration of perovskite in the perovskite precursor solution is 1.5M, the structural formula of the perovskite is FAPbI3, the dosage ratio of perovskite to the additive is 1.5mol:5g, and the solvent is a mixed solution of N,N-dimethylformamide (DMF) / dimethyl sulfoxide (DMSO) / isopropylbenzene hydroperoxide (CHP) with a volume ratio of 80:15:5.

[0059] The preparation method of the above-mentioned perovskite precursor solution has the following specific steps: according to the structural formula of perovskite and the above-mentioned numerical values ​​and ratios, the amount of each raw material is calculated; formamidine hydroiodide (FAI), lead iodide (PbI2) and methylamine chloride (MACl) are weighed and dissolved in a solvent (a mixed solution of N,N-dimethylformamide (DMF) / dimethyl sulfoxide (DMSO) / isopropylbenzene hydroperoxide (CHP) with a volume ratio of 80:15:5), so that the concentration of formamidine hydroiodide (FAI) in the solution is 1.5M, the concentration of lead iodide (PbI2) is 1.5M, and the concentration of methylamine chloride (MACl) is 0.3M, and the solution is cooled, shaken or stirred to dissolve until clear to obtain a solution; take 1mL of a solution, weigh 5mg of ATMP, and dissolve it in 1mL of a solution to obtain a perovskite precursor solution.

[0060] Example 3

[0061] A perovskite precursor solution contains perovskite, a solvent and an additive; the additive is ATMP (aminotrimethylene phosphoric acid, solid, CAS: 6419-19-8, purchased from Aladdin); the concentration of perovskite in the perovskite precursor solution is 1.5M, and the structural formula of perovskite is Cs 0.05 MA 0.1 FA 0.85 Pb(I0.95 Br 0.05 )3, the dosage ratio of perovskite to additive is 1.5 mol:5 g, and the solvent is a DMF / DMSO mixture with a volume ratio of 4:1.

[0062] The preparation method of the above-mentioned perovskite precursor solution has the following specific steps: according to the structural formula of the perovskite and the above-mentioned numerical values ​​and ratios, the amount of each raw material is calculated; formamidine hydroiodide (FAI) and lead iodide (PbI2) are weighed and dissolved in a solvent (DMF / DMSO mixed solution with a volume ratio of 4:1), so that the concentrations of formamidine hydroiodide (FAI) and lead iodide (PbI2) are 1.5M and 1.5M respectively, to obtain a solution No. 1; methylamine bromide (MABr), lead bromide (PbBr2) and methylamine chloride (MACl) are weighed and dissolved in a solvent (DMF / DMSO mixed solution with a volume ratio of 4:1). :1 DMF / DMSO mixture), so that the concentrations of methylamine bromide (MABr), lead bromide (PbBr2) and methylamine chloride (MACl) are 1.5M, 1.5M and 0.5M respectively, to obtain solution No. 2; weigh cesium iodide (CsI) and dissolve it in DMSO solvent to make its concentration 1.5M to obtain solution No. 3; mix solution No. 1, solution No. 2 and solution No. 3 in a volume ratio of 50:18:9 to obtain solution a; take 1mL of solution a, weigh 5mg of ATMP, and dissolve it in 1mL of solution a to obtain a perovskite precursor solution.

[0063] Example 4

[0064] A perovskite precursor solution contains perovskite, a solvent and an additive; the additive is PASP (polyaspartic acid, liquid, CAS: 181828-06-8, purchased from Aladdin); the concentration of perovskite in the perovskite precursor solution is 1.5M, and the structural formula of perovskite is Cs 0.05 MA 0.1 FA 0.85 Pb(I 0.95 Br 0.05 )3, the dosage ratio of perovskite to additive is 1.5 mol:5 g, and the solvent is a DMF / DMSO mixture with a volume ratio of 4:1.

[0065] The preparation method of the above-mentioned perovskite precursor solution has the following specific steps: according to the structural formula of the perovskite and the above-mentioned numerical values ​​and ratios, the amount of each raw material is calculated; formamidine hydroiodide (FAI) and lead iodide (PbI2) are weighed and dissolved in a solvent (DMF / DMSO mixed solution with a volume ratio of 4:1), so that the concentrations of formamidine hydroiodide (FAI) and lead iodide (PbI2) are 1.5M and 1.5M respectively, to obtain a solution No. 1; methylamine bromide (MABr), lead bromide (PbBr2) and methylamine chloride (MACl) are weighed and dissolved in a solvent (DMF / DMSO mixed solution with a volume ratio of 4:1). :1 DMF / DMSO mixture), so that the concentrations of methylamine bromide (MABr), lead bromide (PbBr2) and methylamine chloride (MACl) are 1.5M, 1.5M and 0.5M respectively, to obtain solution No. 2; weigh cesium iodide (CsI) and dissolve it in DMSO solvent to make its concentration 1.5M to obtain solution No. 3; mix solution No. 1, solution No. 2 and solution No. 3 in a volume ratio of 50:18:9 to obtain solution a; take 1mL of solution a, weigh 5mg of PASP, and dissolve it in 1mL of solution a to obtain a perovskite precursor solution.

[0066] Example 5

[0067] A perovskite precursor solution contains perovskite, a solvent and an additive; the additive is BTA (benzotriazole, solid, CAS: 95-14-7, purchased from Aladdin); the concentration of perovskite in the perovskite precursor solution is 1.5M, and the structural formula of perovskite is Cs 0.05 MA 0.1 FA 0.85 Pb (I 0.95 Br 0.05 )3, the dosage ratio of perovskite to additive is 1.5 mol:2 g, and the solvent is a DMF / DMSO mixture with a volume ratio of 4:1.

[0068] The preparation method of the perovskite precursor solution is as follows: According to the structural formula of the perovskite and the above various numerical values and ratios, calculate the amounts of each raw material; Weigh formamidinium hydroiodide (FAI) and lead iodide (PbI2), and dissolve them in a solvent (a DMF / DMSO mixture with a volume ratio of 4:1) to make the concentrations of formamidinium hydroiodide (FAI) and lead iodide (PbI2) 1.5 M and 1.5 M respectively, obtaining a first solution; Weigh methylammonium bromide (MABr), lead bromide (PbBr2) and methylammonium chloride (MACl), and dissolve them in a solvent (a DMF / DMSO mixture with a volume ratio of 4:1) to make the concentrations of methylammonium bromide (MABr), lead bromide (PbBr2) and methylammonium chloride (MACl) 1.5 M, 1.5 M and 0.5 M respectively, obtaining a second solution; Weigh cesium iodide (CsI) and dissolve it in DMSO solvent to make its concentration 1.5 M, obtaining a third solution; Mix the first solution, the second solution and the third solution according to a volume ratio of 50:18:9 to obtain solution a; Take 1 mL of solution a, weigh 2 mg of BTA, and dissolve it in 1 mL of solution a to obtain the perovskite precursor solution.

[0069] Example 6

[0070] A perovskite photovoltaic cell includes a substrate, a first electrode layer, a first charge transport layer, a perovskite light-absorbing layer, a second charge transport layer, and a second electrode layer that are sequentially stacked from bottom to top.

[0071] Among them, the substrate is a glass substrate, the first electrode layer is a transparent conductive layer, the first charge transport layer is a hole transport layer, the perovskite light-absorbing layer is a perovskite thin film, and the second charge transport layer is an electron transport layer.

[0072] The transparent conductive layer is an indium tin oxide (ITO) thin film, the hole transport layer is a self-assembled monolayer film of Me-4PACz, and the perovskite light-absorbing layer is a perovskite thin film prepared from the perovskite precursor solution prepared in Example 1; The electron transport layer is a C 60 thin film, and there is also a tin oxide thin film as a buffer layer on the electron transport layer; The second electrode layer is a single silver thin film.

[0073] The preparation method of the above perovskite photovoltaic cell is as follows:

[0074] 1. Pretreatment: Wash the ITO conductive glass (glass substrate with a transparent conductive layer) with detergent and pure water multiple times, dry it, and then perform plasma treatment for 7 minutes to obtain the substrate / transparent conductive layer.

[0075] 2. Preparation of the hole transport layer: Dissolve Me-4PACz in ethanol to obtain a Me-4PACz solution with a concentration of 0.5 mg / mL; spin-coat the above Me-4PACz solution on the above transparent conductive layer at a speed of 3000 r, with a spin-coating time of 30 s, and anneal at 100 °C for 5 min to obtain the substrate / transparent conductive layer / hole transport layer.

[0076] 3. Preparation of the perovskite light-absorbing layer: Take the perovskite precursor solution prepared in Example 1, drop it on the above hole transport layer, spin-coat for 65 s, and add the antisolvent EA 13 s before the end of spin-coating (spin-coating for 52 s); anneal, anneal at 150 °C for 5 min, and then anneal at 120 °C for 30 min to obtain the substrate / transparent conductive layer / hole transport layer / perovskite light-absorbing layer.

[0077] 4. Preparation of the electron transport layer: Evaporate 20 nm thick C 60 on the above perovskite light-absorbing layer at an evaporation rate of 0.2 Å per second; then continue to deposit 30 nm thick tin oxide using ALD to obtain the substrate / transparent conductive layer / hole transport layer / perovskite light-absorbing layer / electron transport layer.

[0078] 5. Preparation of the second electrode layer: Evaporate an 80 nm thick elemental silver film on the above electron transport layer according to the conventional method to obtain the substrate / transparent conductive layer / hole transport layer / perovskite light-absorbing layer / electron transport layer / second electrode layer, that is, the perovskite photovoltaic cell is obtained.

[0079] Example 7

[0080] A perovskite photovoltaic cell, whose structure and preparation method are basically the same as those in Example 6, the difference is that in step 3 for preparing the perovskite light-absorbing layer, take the perovskite precursor solution prepared in Example 2, drop it on the hole transport layer, spin-coat for 70 s, and add the antisolvent EA 13 s before the end of spin-coating (spin-coating for 57 s); anneal, anneal at 150 °C for 5 min, and then anneal at 120 °C for 30 min to obtain the substrate / transparent conductive layer / hole transport layer / perovskite light-absorbing layer.

[0081] Example 8

[0082] A perovskite photovoltaic cell, whose structure and preparation method are basically the same as those in Example 6, the difference is that in step 3 for preparing the perovskite light-absorbing layer, take the perovskite precursor solution prepared in Example 3, drop it on the hole transport layer, spin-coat for 60 s, and add the antisolvent EA 13 s before the end of spin-coating (spin-coating for 47 s); anneal, anneal at 150 °C for 5 min, and then anneal at 120 °C for 30 min to obtain the substrate / transparent conductive layer / hole transport layer / perovskite light-absorbing layer.

[0083] Example 9

[0084] A perovskite photovoltaic cell has a structure and preparation method that are basically the same as those in Example 6. The difference is that in step 3 of preparing the perovskite light-absorbing layer, the perovskite precursor solution prepared in Example 4 is taken, dropped on the hole transport layer, spin-coated for 60 s, and the antisolvent EA is added 13 s before the end of spin-coating (spin-coating for 47 s); annealing is carried out, annealing is carried out at 150 °C for 5 min, and then annealing is carried out at 120 °C for 30 min to obtain a substrate / transparent conductive layer / hole transport layer / perovskite light-absorbing layer.

[0085] Example 10

[0086] A perovskite photovoltaic cell has a structure and preparation method that are basically the same as those in Example 6. The difference is that in step 3 of preparing the perovskite light-absorbing layer, the perovskite precursor solution prepared in Example 5 is taken, dropped on the hole transport layer, spin-coated for 60 s, and the antisolvent EA is added 13 s before the end of spin-coating (spin-coating for 47 s); annealing is carried out, annealing is carried out at 150 °C for 5 min, and then annealing is carried out at 120 °C for 30 min to obtain a substrate / transparent conductive layer / hole transport layer / perovskite light-absorbing layer.

[0087] Comparative Example 1

[0088] A perovskite precursor solution is basically the same as that in Example 1, except that it does not contain additives.

[0089] Comparative Example 2

[0090] A perovskite precursor solution is basically the same as that in Example 2, except that it does not contain additives.

[0091] Comparative Example 3

[0092] A perovskite precursor solution is basically the same as that in Example 3, except that it does not contain additives.

[0093] Comparative Example 4

[0094] A perovskite photovoltaic cell has a structure and preparation method that are basically the same as those in Example 6. The difference is that the perovskite precursor solution prepared in Comparative Example 1 is used in step 3 of preparing the perovskite light-absorbing layer.

[0095] Experimental Example 1

[0096] 1. XRD detection was carried out on perovskite thin films made from perovskite precursor solutions at different aging stages.

[0097] (1)Take the perovskite precursor solutions of Example 1 and Comparative Example 1 respectively, place them in the air, take the perovskite precursor solutions on the 1st day, 10th day, 20th day, 30th day, and 40th day respectively, and prepare perovskite thin films on the ITO substrate according to the method of Example 6. Use a TDM-20 X-ray Mini Diffractometer to detect the perovskite thin films to obtain XRD patterns.

[0098] The test results are as Figure 1 and Figure 2 shown. The thin film made from the solution of Example 1 on the 40th day of storage is still black and no yellow phase appears, indicating that the perovskite precursor solution of Example 1 is not affected by the environment, has long-term storage stability, is stable and not easily aged; the solution of Comparative Example 1 shows a yellow phase in the thin film prepared on the 40th day of storage.

[0099] (2)Take the perovskite precursor solutions of Example 2 and Comparative Example 2 respectively, place them in the air, take the perovskite precursor solutions on the 1st day, 8th day, and 16th day respectively, and prepare perovskite thin films on the ITO substrate according to the method of Example 7. Use a TDM-20 X-ray Mini Diffractometer to detect the perovskite thin films to obtain XRD patterns.

[0100] The test results are as Figure 3 and Figure 4 shown. Although a yellow phase appears in the thin film made from the solution of Example 2 on the 16th day of storage in the air, there are still more black phases with photovoltaic effect, indicating that the perovskite precursor solution of Example 2 has long-term storage stability, is stable and not easily aged; the thin film prepared from the solution of Comparative Example 2 on the 16th day of storage in the air is completely an ineffective yellow phase without a black phase with photovoltaic effect.

[0101] (3)Take the perovskite precursor solutions of Example 3 and Comparative Example 3 respectively, place them in the air, take the perovskite precursor solutions on the 1st day, 10th day, 20th day, and 40th day respectively, and prepare perovskite thin films on the ITO substrate according to the method of Example 8. Use a TDM-20 X-ray Mini Diffractometer to detect the perovskite thin films to obtain XRD patterns.

[0102] The test results are as Figure 5 and Figure 6As shown, the film prepared from the solution of Example 3 on the 40th day after being placed in air is still black and no yellow phase appears, indicating that the perovskite precursor solution of Example 3 is not affected by the environment, has long-term storage properties, is stable and not easily aged; the film prepared from the solution of Comparative Example 3 on the 20th day after being placed in air has started to show a yellow phase, and the film prepared on the 40th day has no black phase with photovoltaic effect but a completely ineffective yellow phase, indicating that the perovskite precursor solution of Comparative Example 3 is more easily aged and not suitable for long-term storage.

[0103] (4)Take the perovskite precursor solution of Example 4, place it in air, take the perovskite precursor solution on the 0th day, 20th day, and 40th day respectively, and prepare perovskite films on ITO substrates according to the method of Example 9. Use a TDM-20 X-ray Mini Diffractometer to detect the perovskite films to obtain XRD patterns.

[0104] The detection results are as Figure 7 shown. The film prepared from the solution of Example 4 on the 40th day after being placed in air is still black and no yellow phase appears, indicating that the perovskite precursor solution of Example 4 is not affected by the environment, has long-term storage properties, is stable and not easily aged.

[0105] (5)Take the perovskite precursor solution of Example 5, place it in air, take the perovskite precursor solution on the 0th day, 20th day, and 40th day respectively, and prepare perovskite films on ITO substrates according to the method of Example 10. Use a TDM-20 X-ray Mini Diffractometer to detect the perovskite films to obtain XRD patterns.

[0106] The detection results are as Figure 8 shown. The film prepared from the solution of Example 5 on the 40th day after being placed in air is mainly black and only slightly shows some inconspicuous yellow phases, indicating that the perovskite precursor solution of Example 5 is not affected by the environment, has long-term storage properties, is stable and not easily aged.

[0107] From the above experimental comparisons, it can be seen that adding the additive of the present invention to the precursor solutions containing different types of perovskites all has the effect of delaying aging; adding different types of additives of the present invention to the precursor solutions containing the same type of perovskite all has the effect of delaying aging.

[0108] 2. Observe the appearance of perovskite films made from perovskite precursor solutions at multiple aging stages.

[0109] Observation objects: (1) The perovskite precursor solutions of Example 1 and Comparative Example 1 were placed in air. The perovskite precursor solutions were taken on the 0th day, 20th day, and 40th day respectively, and perovskite thin films were prepared on ITO substrates according to the method of Example 6; (2) The perovskite precursor solutions of Example 2 and Comparative Example 2 were placed in air. The perovskite precursor solutions were taken on the 1st day, 8th day, and 16th day respectively, and perovskite thin films were prepared on ITO substrates according to the method of Example 7; (3) The perovskite precursor solutions of Example 3 and Comparative Example 3 were placed in air. The perovskite precursor solutions were taken on the 1st day and 40th day respectively, and perovskite thin films were prepared on ITO substrates according to the method of Example 8.

[0110] The observation results are as Figures 9 - 11 shown. It can be seen that compared with the comparative examples, the thin films made from the perovskite precursor solutions added with the additive of the present invention are still in a black phase after aging, indicating that the additive of the present invention has the effect of delaying aging on the precursor solutions containing different types of perovskites.

[0111] Experimental Example 2

[0112] The I-V characteristics of perovskite photovoltaic modules were detected using an LSS-55 solar simulator.

[0113] Detection objects: The perovskite precursor solutions of Examples 1 to 5 and Comparative Examples 1 to 3 were placed in air for several days, and perovskite photovoltaic cells were prepared according to the methods of Examples 6 to 10 respectively. Then, the photovoltaic cells were encapsulated into perovskite photovoltaic modules according to the conventional method.

[0114] The detection results are as Figures 12 - 19 shown. For the module prepared from the solution of Example 1 on the 25th day of being placed in air, no performance degradation occurred. However, for the module prepared from the solution of Comparative Example 1 on the 18th day of being placed in air, performance degradation began, indicating that the solution of Example 1 is not easily aged and can be stored for a long time. For the module prepared from the solution of Example 2 on the 8th day of being placed in air, no performance degradation occurred, and the module still had relatively ideal optoelectronic performance on the 16th day. However, for the module prepared from the solution of Comparative Example 2 on the 8th day of being placed in air, performance degradation began, and the module had no optoelectronic performance at all on the 16th day, indicating that the solution of Example 2 is not easily aged and can be stored for a long time. For the module prepared from the solution of Example 3 on the 25th day of being placed in air, no performance degradation occurred. However, for the module prepared from the solution of Comparative Example 3 on the 18th day of being placed in air, performance degradation began, indicating that the solution of Example 3 is not easily aged and can be stored for a long time. For the module prepared from the solution of Example 4 on the 40th day of being placed in air, no performance degradation occurred. For the module prepared from the solution of Example 5, the performance slightly decreased on the 20th day of being placed in air, and performance degradation occurred on the 40th day.

[0115] It can be seen by comparison that the perovskite precursor solution added with the additive of the present invention still has good photovoltaic characteristics after being aged and made into a photovoltaic module.

[0116] Through the above experiments, it can be seen that the comprehensive performance of the perovskite precursor solution in Example 1 is the best. Therefore, for the following further verification tests, the perovskite precursor solution prepared in Example 1 and the perovskite photovoltaic cell prepared in Example 6 are used.

[0117] Experimental Example 3

[0118] 1. Observe the appearance of the solution.

[0119] Observe the color changes of the perovskite precursor solutions prepared in Example 1 and Comparative Example 1 on the 0th day, 10th day, 20th day, and 40th day. The results are as Figure 20 shown. It can be clearly seen that compared with Comparative Example 1, the perovskite precursor solution of the present invention (labeled W on the bottle body) has a lower degree of color deepening over time, indicating better storage stability.

[0120] 2. Perform PL detection on the perovskite thin film.

[0121] Take the perovskite precursor solutions of Example 1 and Comparative Example 1, place them in the air, and take the perovskite precursor solutions on the 1st day, 5th day, 9th day, and 13th day respectively. Then prepare perovskite thin films on the ITO substrate according to the method of Example 6 and perform detection using an AVANTES photoluminescence detector to obtain PL spectra.

[0122] The detection results are as Figure 21 and Figure 22 shown. The PL spectrum of the thin film corresponding to Example 1 shows that the visible light emission intensity decreases slowly, indicating that the photovoltaic effect of the perovskite thin film corresponding to Example 1 fails slowly; the PL spectrum of the thin film corresponding to Comparative Example 1 shows that the visible light emission intensity is decreasing, indicating that the photovoltaic effect of the perovskite thin film corresponding to Comparative Example 1 is decreasing.

[0123] 3. Detect the device performance of the perovskite photovoltaic cell.

[0124] (1) Use an LSS-55 solar simulator to detect the perovskite photovoltaic cell devices prepared in Example 6 and Comparative Example 4. The detection results are as Figure 23 shown. The detection results corresponding to Example 6 are marked as W, and the detection results corresponding to Comparative Example 4 are marked as WO, indicating that the performance of the photovoltaic cell device of the present invention is improved compared with Comparative Example 4.

[0125] (2) Take the perovskite precursor solutions of Example 1 and Comparative Example 1, place them in the air, and take the perovskite precursor solutions on the 1st day, 10th day, 20th day, 30th day, and 40th day respectively, and prepare perovskite photovoltaic cells according to the methods of Example 6 and Comparative Example 4. Use the LSS-55 solar simulator to detect the photovoltaic cell devices respectively, and obtain the statistical results of the relationship between the electrical performance parameters of the perovskite photovoltaic cells corresponding to Example 1 and the Comparative Example and the solution storage time. The detection results are as Figure 24 and Figure 25 shown, Figure 24 The numerical changes in indicate that the perovskite precursor solution of Example 1 did not show aging phenomenon on the 40th day, and the performance of the photovoltaic device prepared after being placed in the air for 40 days was still better than that of the photovoltaic device prepared with the fresh solution; Figure 25 The numerical changes in indicate that the perovskite precursor solution of Comparative Example 1 had aged on the 30th day and aged rapidly within 10 days.

[0126] (3) Take the perovskite precursor solutions of Example 1 and Comparative Example 1, place them in the air, and take the perovskite precursor solutions on the 1st, 2nd, 3rd, 4th, 5th, 7th, 8th, 9th, 10th, 18th, 21st, 25th, 30th, 35th, 40th day respectively, and prepare perovskite photovoltaic cells according to the methods of Example 6 and Comparative Example 4. Use the LSS-55 solar simulator to detect the photovoltaic cell devices respectively, and obtain the change relationship of the photoelectric conversion efficiency of the perovskite photovoltaic cell with the solution storage time. The detection results are as Figure 26 shown. The detection results corresponding to Example 1 are marked as W, and the detection results corresponding to Comparative Example 1 are marked as WO, indicating that the perovskite precursor solution of Example 1 is less prone to aging.

[0127] (4) Use the AP-HX-408C6 85°C & 85%RH high-temperature and high-humidity equipment and the LSS-55 solar simulator to conduct damp-heat aging tests on the perovskite photovoltaic cell devices of Example 6 and Comparative Example 4 respectively. The detection results are as Figure 27 shown. The detection results corresponding to Example 1 are marked as W, and the detection results corresponding to Comparative Example 1 are marked as WO, indicating that the photovoltaic device prepared in Example 6 has better stability.

[0128] (5) After placing the perovskite precursor solutions of Example 1 and Comparative Example 1 under AM1.5 illumination for 3 days, prepare perovskite photovoltaic cells according to the methods of Example 6 and Comparative Example 4 respectively, and use the LSS-55 solar simulator for detection to obtain the comparison of the statistical results of the photoelectric conversion efficiency of the perovskite photovoltaic cells. The detection results are as Figure 28 shown. The detection results corresponding to Example 1 are marked as W, and the detection results corresponding to Comparative Example 1 are marked as WO, indicating that the perovskite precursor solution of Example 1 is less prone to aging due to environmental influence.

[0129] (6) After placing the perovskite precursor solutions of Example 1 and Comparative Example 1 at 85 °C and 45% relative humidity for 3 days, perovskite photovoltaic cells were prepared according to the methods of Example 6 and Comparative Example 4 respectively, and detected using an LSS-55 solar simulator to obtain a comparison of the statistical results of the photoelectric conversion efficiency of the perovskite photovoltaic cells. The detection results are as Figure 29 shown. The detection result corresponding to Example 1 is marked as W, and the detection result corresponding to Comparative Example 1 is marked as WO, indicating that the perovskite precursor solution of Example 1 is less susceptible to environmental influence and aging.

[0130] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as the scope described in this specification.

[0131] The above-described embodiments only represent several implementation manners of the present invention. The description is relatively specific and detailed, but it should not be construed as a limitation on the scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the present invention patent shall be subject to the appended claims.

Claims

1. A perovskite precursor solution, characterized in that, It contains perovskite, a solvent and an additive; the additive contains a corrosion inhibitor; the dosage ratio of the perovskite to the additive in the perovskite precursor solution is (1 - 10) mol : (0.5 - 25) g.

2. The perovskite precursor solution according to claim 1, wherein The concentration of the perovskite is 0.2M - 2M.

3. The perovskite precursor solution according to claim 1, wherein, The corrosion inhibitor includes at least one of organic phosphorus corrosion inhibitors, phosphono-carboxylic acid copolymer corrosion inhibitors, and metal-specific corrosion inhibitors.

4. The perovskite precursor solution according to claim 3, wherein The organic phosphorus corrosion inhibitor includes at least one of amino trimethylene phosphonic acid, hydroxyethylidene diphosphonic acid, diethylenetriamine pentamethylene phosphonic acid, ethylenediamine tetramethyl phosphonic acid, and 2-hydroxyphosphonoacetic acid; the phosphono-carboxylic acid copolymer corrosion inhibitor includes at least one of polyepoxysuccinic acid and polyaspartic acid; the metal-specific corrosion inhibitor includes at least one of methylene bisthiocyanate, benzotriazole, and methylbenzotriazole.

5. The perovskite precursor solution according to claim 1, wherein The structure of the perovskite is ABX3, where A is a monovalent cation, B is a divalent cation, and X is a monovalent anion; A includes at least one of methylamine, formamidine, cesium, rubidium, PEA + , PMA + , OA + , and the like; B includes at least one of lead, tin, antimony, gallium, or strontium; X includes at least one of fluorine, iodine, bromine, chlorine, BF4 - , BF3 - .

6. The preparation method of the perovskite precursor solution according to any one of claims 1 to 5, characterized in that, It includes the following steps: Calculate the dosages of each raw material, weigh the raw materials according to the ratio, and dissolve them in the solvent to obtain the product.

7. A perovskite photovoltaic cell, characterized in that, It includes a perovskite light-absorbing layer, and the perovskite light-absorbing layer includes a perovskite thin film, and the perovskite thin film is prepared from the perovskite precursor solution according to any one of claims 1 - 5.

8. The perovskite photovoltaic cell according to claim 7, wherein It includes a first electrode layer, a first charge transport layer, a perovskite light-absorbing layer, a second charge transport layer, and a second electrode layer which are stacked in sequence from bottom to top.

9. The preparation method of the perovskite photovoltaic cell according to any one of claims 7 to 8, characterized in that, It includes the following steps: Prepare a perovskite light-absorbing layer; the method for preparing the perovskite light-absorbing layer is specifically: deposit the perovskite precursor solution according to any one of claims 1 - 5 into a film and anneal it to obtain the product.

10. The preparation method of the perovskite photovoltaic cell according to claim 9, characterized in that, It includes the following steps: Prepare a first charge transport layer; prepare a perovskite light-absorbing layer; Prepare a second charge transport layer; prepare a second electrode layer.

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