Perovskite solution, preparation method and application thereof, and perovskite battery

Abstract

The invention relates to a perovskite solution, a preparation method and application thereof, and a perovskite battery. The perovskite solution comprises a perovskite precursor and an additive, the additives are dibasic acid ester, nylon acid diisobutyl ester, iodobenzene diacetic acid, diisopropanolamine, diethanol amine, diisodecyl adipate, dibutyl adipate, dimethylacetamide, dioctyl adipate, diisobutyl glutarate, dimethyl sebacate, diisobutyl adipate, diisobutyl succinate and triethyl citrate; and at least one of tributyl citrate. According to the perovskite solution disclosed by the invention, the bromide ion-free or low-bromide ion perovskite precursor can form a black-phase film with good stability by adding the additive, so that the photoelectric conversion efficiency of a perovskite photovoltaic device is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of solar cells, and in particular to a perovskite solution, a preparation method and application thereof, and a perovskite cell. Background Art

[0002] Perovskite solar cells are solar cells that use perovskite-type organic-inorganic hybrid metal halide semiconductors as light-absorbing materials. They have excellent photoelectric properties such as high absorption coefficient, wide absorption range, adjustable band gap, and long carrier diffusion length. They are a renewable clean energy source and are of great significance to the sustainable development of mankind.

[0003] Among them, formamidinium lead iodine perovskite has a narrower bandgap and higher photoelectric conversion efficiency, and has been widely used in the preparation of high-performance solar cells. However, the α-FAPbI3 phase with photoelectric performance exists in a metastable state, and it is not easy to form a stable black phase in the atmospheric environment. The formed black phase is easily transformed into a non-optically active phase at room temperature, which in turn affects the photoelectric conversion efficiency of perovskite solar cells. The polycation perovskite containing formamidinium faces the same problem because it is mainly based on the structure of formamidinium lead iodine perovskite, and a small amount of other cations will not improve the crystallinity of formamidinium lead iodine perovskite.

[0004] Therefore, there is an urgent need to develop a formamidine-based solar cell with high photoelectric conversion efficiency and good stability. Summary of the invention

[0005] Based on this, it is necessary to provide a perovskite solution, a preparation method and application thereof, and a perovskite battery to address the problem that the formamidinium-based perovskite film is very easy to transform into a non-optically active phase under high humidity conditions and reduce the stability of the film and the efficiency of the device.

[0006] A perovskite solution comprises a perovskite precursor and an additive; the additive is at least one of dibasic acid ester (DBE), diisobutyl nylonate (DBE-IB), iodobenzenediacetic acid (DIB), diisopropanolamine (DIPA), diethanolamine (DEA), diisodecyl adipate (DIDA), dibutyl adipate (DBA), dimethylacetamide (DMA), dioctyl adipate (DOA), diisobutyl glutarate, dimethyl sebacate, diisobutyl adipate, diisobutyl succinate, triethyl citrate (TEC), and tributyl citrate (TBC).

[0007] The above-mentioned perovskite solution, by adding additives, enables the bromide-free or low-bromide-ion perovskite precursor to form a black phase film with good stability, thereby improving the photoelectric conversion efficiency of the perovskite photovoltaic device.

[0008] In one embodiment, the volume content of the additive in the perovskite solution is 1% to 30%.

[0009] In one embodiment, the concentration of the perovskite precursor in the perovskite solution is 0.8-1.8 mol / L.

[0010] In one embodiment, the additive comprises a first additive and a second additive; the first additive is at least one of diisobutyl glutarate, diisobutyl succinate, and diisobutyl adipate; the second additive is at least one of dimethyl sebacate, diisodecyl adipate, and dimethylacetamide.

[0011] In one embodiment, the first additive is diisobutyl glutarate, and the second additive is dimethyl sebacate; in the additives, the volume ratio of the first additive to the second additive is 1:19 to 19:1.

[0012] In one embodiment, the perovskite solution further comprises an organic solvent; the organic solvent is at least one of N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), cumene hydroperoxide (CHP), 2-mercaptoimidazole (2Me), N-methylpyrrolidone (NMP), tetramethylene sulfoxide (TMSO), and tetrahydrofuran (THF).

[0013] In one embodiment, the structure of the perovskite precursor is ABX3; A is at least one of methylamine cation, cesium ion, rubidium ion, and formamidinium cation; B is at least one of divalent lead ion and divalent tin ion; and X is a monovalent iodine ion.

[0014] The present invention also provides a method for preparing the perovskite solution, comprising the following steps: mixing the additive with a solvent to obtain a mixed solution; and dissolving a perovskite precursor material in the mixed solution to obtain.

[0015] In one embodiment, the perovskite precursor material includes at least one of FAI, FABr, MAI, MABr, CsI, RbI, PbI2, PbBr2, and PbCl2.

[0016] The present invention also provides a perovskite battery, comprising a perovskite layer, wherein the perovskite layer is prepared from the perovskite solution as described above.

[0017] In one of the embodiments, the perovskite cell includes the following structure stacked in sequence from bottom to top: a transparent conductive substrate, a first charge transport layer, a perovskite layer, a second charge transport layer, and a top electrode.

[0018] The present invention also provides a method for preparing the perovskite battery, which is characterized in that it includes the following steps: sequentially preparing a first charge transport layer, a perovskite layer, a second charge transport layer, and a top electrode on a transparent conductive substrate.

[0019] The present invention also provides an application of the perovskite battery in preparing a power generation device and / or an energy storage device and / or an electricity consumption device.

[0020] The present invention also provides an application of the perovskite solution in preparing a power generation device and / or an energy storage device and / or an electricity consumption device.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] The invention discloses a perovskite solution, a preparation method and application thereof, and a perovskite cell. By adding additives, a perovskite precursor without bromide ions or with low bromide ions can form a black phase film with good stability, thereby improving the photoelectric conversion efficiency of the perovskite photovoltaic device. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is a comparison of the appearance of the perovskite films prepared in Example 4 (with) and Comparative Example 2 (without) in Experimental Example 1;

[0024] Figure 2 XRD comparison diagram of the perovskite film prepared in Example 4 (with) and Comparative Example 2 (without) in Experimental Example 2;

[0025] Figure 3 A comparison chart of the photoluminescence spectra (PL spectra) of the perovskite films prepared in Example 4 (with) and Comparative Example 2 (without) in Experimental Example 3;

[0026] Figure 4 This is a comparison chart of EQE of the perovskite battery devices prepared in Example 4 (with) and Comparative Example 2 (without) in Experimental Example 4;

[0027] Figure 5 This is a comparison chart of the current-voltage detection results of the perovskite battery devices prepared in Example 4 (with) and Comparative Example 2 (without) in Experimental Example 5. DETAILED DESCRIPTION

[0028] 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.

[0029] 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.

[0030] The reagents used in the following examples are commercially available unless otherwise specified; the methods used in the following examples are conventionally achievable unless otherwise specified; the preparation steps in the following examples are carried out at room temperature and pressure unless otherwise specified.

[0031] Example 1

[0032] A perovskite solution is prepared, the preparation method comprising the following steps:

[0033] (1) N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), cumene hydroperoxide (CHP), diisobutyl glutarate (CAS No. 136499-29-1, purchased from Aladdin), and dimethyl sebacate (CAS No. 106-79-6, purchased from Aladdin) were mixed in a volume ratio of 80:10:9:0.6:0.4 to obtain a mixed solution.

[0034] (2) Take 1 mL of the above mixed solution and dissolve the perovskite precursor material and methylamine chloride in the mixed solution according to the following molar concentrations: 0.03 M rubidium iodide (RbI), 1.5 M formamidine hydroiodide (FAI), 1.5 M lead iodide (PbI2) and 0.3 M methylamine chloride (MACl) to obtain a perovskite solution.

[0035] The perovskite structure prepared in this embodiment is (RbPbI3) 0.02 (FAPbI3) 0.98 , the band gap is 1.52eV.

[0036] Example 2

[0037] A perovskite solution is prepared, the preparation method comprising the following steps:

[0038] (1) N,N-dimethylformamide (DMF), 2-mercaptoimidazole (2Me), diisobutyl glutarate, and dimethyl sebacate were mixed in a volume ratio of 85:10:4:1 to obtain a mixed solution.

[0039] (2) Take 1 mL of the above mixed solution and dissolve the perovskite precursor material and methylamine chloride in the mixed solution according to the following molar concentrations: 0.03 M rubidium iodide (RbI), 1.5 M formamidine hydroiodide (FAI), 1.5 M lead iodide (PbI2) and 0.3 M methylamine chloride (MACl) to obtain a perovskite solution.

[0040] The perovskite structure prepared in this embodiment is (RbPbI3) 0.02 (FAPbI3) 0.98 , the band gap is 1.52eV.

[0041] Example 3

[0042] A perovskite solution is prepared, the preparation method comprising the following steps:

[0043] (1) N,N-dimethylformamide (DMF), tetramethylene sulfoxide (TMSO), N-methylpyrrolidone (NMP), diisobutyl glutarate, and dimethyl sebacate were mixed in a volume ratio of 70:20:5:4:1 to obtain a mixed solution.

[0044] (2) Take 1 mL of the above mixed solution and dissolve the perovskite precursor material and methylamine chloride in the mixed solution according to the following molar concentrations: 0.03 M rubidium iodide (RbI), 1.5 M formamidine hydroiodide (FAI), 1.5 M lead iodide (PbI2) and 0.3 M methylamine chloride (MACl) to obtain a perovskite solution.

[0045] The perovskite structure prepared in this embodiment is (RbPbI3) 0.02 (FAPbI3) 0.98 , the band gap is 1.52eV.

[0046] Example 4

[0047] The preparation area is 0.09 cm 2 The perovskite battery, the preparation method comprises the following steps:

[0048] (1) Substrate treatment: Soak a 2.5 cm*2.5 cm glass substrate in a cleaning agent and perform ultrasonic cleaning for 15 min, then use deionized water to clean it for 15 min, and repeat this cycle twice; use an air gun to blow dry the glass substrate and then place it in a UV treatment box for UV irradiation for 10 min to obtain a treated substrate.

[0049] (2) Preparation of hole transport layer: Prepare a solution of 0.5 mg Me-4PACz dissolved in 1 mL ethanol, take 100 μL and drop it on the above-treated substrate, spin-coat it at a speed of 30,000 r / min for 30 s, and then transfer it to a hot plate at 100°C and heat it for 5 min to obtain a hole transport layer.

[0050] (3) Preparation of perovskite layer: The perovskite solution prepared in Example 1 was dropped onto the hole transport layer, and then scraped (at a speed of 1.5 m / s) to evenly coat the solution on the hole transport layer to form a wet film. After the film was obtained, annealing was performed at a temperature of 130° C. for 15 min to obtain a perovskite layer (perovskite film).

[0051] (4) Preparation of electron transport layer: 30 nm thick C 60 , and then use atomic layer deposition to deposit 20nm thick tin oxide to obtain an electron transport layer.

[0052] (5) Preparation of top electrode: A 20 nm thick silver electrode (with an aperture area of ​​0.09 cm) was evaporated on the above electron transport layer. 2 mask), the area is 0.09cm 2 of perovskite batteries.

[0053] Example 5

[0054] The preparation area is 0.09 cm 2 The preparation method of the perovskite battery is basically the same as that of Example 4, except that in step (3) of preparing the perovskite layer, the perovskite solution prepared in Example 2 is dripped onto the hole transport layer.

[0055] Example 6

[0056] The preparation area is 0.09 cm 2 The preparation method of the perovskite cell is basically the same as that of Example 4, except that in step (3) of preparing the perovskite layer, the perovskite solution prepared in Example 3 is dripped onto the hole transport layer.

[0057] Comparative Example 1

[0058] The perovskite solution was prepared in the same manner as in Example 1, except that diisobutyl glutarate and dimethyl sebacate were not added in step (1), and the volume ratio of N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and isopropylbenzene hydroperoxide (CHP) was 80:15:5.

[0059] Comparative Example 2

[0060] The preparation area is 0.09 cm 2 The preparation method of the perovskite battery is basically the same as that of Example 4, except that in step (3) of preparing the perovskite layer, the perovskite solution prepared in Comparative Example 1 is dripped onto the hole transport layer.

[0061] Experimental Example 1

[0062] Compare the appearance of the perovskite film obtained in step (3) of Example 4 and Comparative Example 2.

[0063] Test results such as Figure 1 As shown, it can be seen that the perovskite film (without) prepared in comparative example 2 does not form a black phase with photoelectric properties very well; while the perovskite film (with) prepared in example 4 can be seen to be in a black and bright state, indicating that a better black phase perovskite film is formed.

[0064] Experimental Example 2

[0065] The perovskite films obtained in step (3) of Example 4 and Comparative Example 2 were respectively detected using a TDM-20 desktop X-ray diffraction spectrometer.

[0066] Test results such as Figure 2 As shown, the perovskite film (without) prepared in Comparative Example 2 is a state where a black phase and a yellow phase coexist and the crystallinity is not high, while the perovskite film (with) prepared in Example 4 does not have a yellow phase and has a very high crystallinity.

[0067] Experimental Example 3

[0068] The perovskite films obtained in step (3) of Example 4 and Comparative Example 2 were respectively detected using a photoluminescence detector.

[0069] Test results such as Figure 3 As shown, the structure is (RbPbI3) 0.02 (FAPbI3) 0.98 The band gap of the perovskite is 1.52 eV, and the photoluminescence spectrum of the perovskite film prepared in Example 4 (with) is significantly higher than that of Comparative Example 2 (without), indicating that the perovskite film prepared in Example 4 can generate more photogenerated electron-hole pairs after being irradiated with light.

[0070] Experimental Example 4

[0071] The perovskite cell devices prepared in Example 4 and Comparative Example 2 were tested using an external quantum efficiency tester (QE).

[0072] Test results such as Figure 4 As shown, it can be seen that the quantum efficiency of the perovskite battery prepared in Example 4 (with) is significantly higher than that of Comparative Example 2 (without), indicating that the perovskite battery prepared in Example 4 has a higher integrated current density, which is consistent with the detection results of Experimental Example 3.

[0073] Experimental Example 5

[0074] The perovskite cell devices prepared in Example 4 and Comparative Example 2 were tested using a solar simulator (Newport Oriel ORIEL-SOI3A).

[0075] Test results such as Figure 5 As shown, the perovskite cell (with) prepared in Example 4 has very good photoelectric activity and photoelectric conversion efficiency, while the perovskite cell (without) prepared in Comparative Example 2 has very poor photoelectric conversion efficiency due to the presence of the yellow phase.

[0076] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, 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, they should be considered to be within the scope of this specification.

[0077] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A perovskite solution, characterized in that: Contains perovskite precursors and additives; The additive is at least one of dibasic acid ester, diisobutyl nylonate, iodophenyldiacetic acid, diisopropanolamine, diethanolamine, diisodecyl adipate, dibutyl adipate, dimethylacetamide, dioctyl adipate, diisobutyl glutarate, dimethyl sebacate, diisobutyl adipate, diisobutyl succinate, triethyl citrate, and tributyl citrate.

2. The perovskite solution according to claim 1, characterized in that The volume content of the additive in the perovskite solution is 1% to 30%.

3. The perovskite solution according to claim 1, characterized in that The additives include a first additive and a second additive; The first additive is at least one of diisobutyl glutarate, diisobutyl succinate, and diisobutyl adipate; The second additive is at least one of dimethyl sebacate, diisodecyl adipate, and dimethylacetamide.

4. The perovskite solution according to claim 3, characterized in that The first additive is diisobutyl glutarate, and the second additive is dimethyl sebacate; in the additives, the volume ratio of the first additive to the second additive is 1:19 to 19:

1.

5. The perovskite solution according to claim 1, characterized in that It also contains an organic solvent; the organic solvent is at least one of N,N-dimethylformamide, dimethyl sulfoxide, cumene hydroperoxide, 2-mercaptoimidazole, N-methylpyrrolidone, tetramethylene sulfoxide and tetrahydrofuran.

6. The perovskite solution according to any one of claims 1 to 5, characterized in that The structure of the perovskite precursor is ABX3; The A is at least one of methylamine cation, cesium ion, rubidium ion, and formamidinium cation; the B is at least one of divalent lead ion and divalent tin ion; and the X is a monovalent iodine ion.

7. A method for preparing a perovskite solution according to any one of claims 1 to 6, characterized in that: The method comprises the following steps: mixing the additive with a solvent to obtain a mixed solution; and dissolving a perovskite precursor material in the mixed solution to obtain the product.

8. A perovskite battery, characterized in that: Comprising a perovskite layer, wherein the perovskite layer is prepared from the perovskite solution according to any one of claims 1 to 6.

9. A method for preparing a perovskite battery as claimed in claim 8, characterized in that: The following steps are involved: The first charge transport layer, the perovskite layer, the second charge transport layer and the top electrode are sequentially prepared on a transparent conductive substrate.

10. Use of the perovskite cell according to claim 8 in preparing a power generation device and / or an energy storage device and / or an electrical device.

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