High-efficiency all-inorganic transmission layer perovskite solar cell in air and preparation method thereof

Abstract

The invention discloses an in-air high-efficiency full-inorganic transmission layer perovskite solar cell and a preparation method thereof, the perovskite solar cell comprises a glass substrate, a NiOx layer, a PVK layer, a SnO2 layer and an electrode which are stacked in sequence, and the preparation method comprises the following steps: (1) cleaning ITO conductive glass; (2) sequentially spin-coating the NiOx layer, the perovskite layer and the SnO2 layer on the ITO conductive glass; and (3) evaporating an electrode. According to the method, the high-efficiency perovskite solar cell is prepared by utilizing a layer-by-layer spin coating process in the air, the process is simple, the operation is convenient, high-cost equipment such as a glove box is not needed, and highly toxic chemicals are not used. According to the perovskite solar cell device with the area of 0.0707 cm < 2 > prepared by the preparation method, the highest efficiency reaches 20.1%; and the maximum efficiency of the prepared large-area battery with the area of 1cm < 2 > reaches 14.6%.

Description

TECHNICAL FIELD

[0001] The present application relates to a perovskite solar cell and a preparation method thereof, in particular to an air high-efficiency all-inorganic transport layer perovskite solar cell and a preparation method thereof. BACKGROUND

[0002] With the increasing of global population, the energy crisis is becoming more and more serious. Non-renewable energy sources such as fossil energy are facing depletion, which brings great challenges to the sustainable development of human beings. Under this background, finding and using clean renewable energy has become an important task.

[0003] Solar energy is a kind of renewable energy that can be taken without exhaustion and used without depletion. Using solar energy to generate electricity instead of traditional thermal power generation not only reduces pollution but also reduces the consumption of fossil energy. Solar cells have undergone several generations of revolution, and the most widely used non-silicon cell is the perovskite solar cell. However, the production process of the perovskite solar cell is more environmentally friendly than that of the silicon cell. Since its inception, its photoelectric conversion efficiency has soared from 3.8% to 26.41% in just a decade, making it the fastest developing photovoltaic device to date. This perovskite material suitable for high-efficiency photovoltaic devices has caused a huge revolution in scientific research and optoelectronic industry due to its excellent light absorption capacity and adjustable band gap. However, the perovskite layer will decompose when it comes into contact with water, so its lifespan in the air is relatively short. In addition, expensive equipment is needed in the preparation process, making the cost of the perovskite solar cell high. These two factors are important bottlenecks restricting the commercialization of the perovskite solar cell. How to reduce the manufacturing cost and manufacture a stable perovskite solar cell in the air has become a difficult problem that researchers need to solve urgently. SUMMARY

[0004] The present application aims to provide an all-inorganic transport layer perovskite solar cell with high efficiency and stability in the air; another object of the present application is to provide a preparation method of an air high-efficiency all-inorganic transport layer perovskite solar cell with simple process and low cost.

[0005] Technical scheme: The air high-efficiency all-inorganic transport layer perovskite solar cell provided by the present application comprises a glass substrate, a NiO x layer, a PVK layer, a SnO2 layer and an electrode which are stacked in sequence.

[0006] Further, the thickness of the NiO x layer is 10-30 nm, the thickness of the PVK layer is 200-500 nm, and the thickness of the SnO2 layer is 10-30 nm.

[0007] The preparation method of the air high-efficiency all-inorganic transport layer perovskite solar cell comprises the following steps:

[0008] (1) cleaning ITO conductive glass;

[0009] (2) spin coating NiO x layer, perovskite (hereinafter referred to as PVK) layer, SnO2 layer on the ITO conductive glass in turn;

[0010] (3) evaporating electrode.

[0011] Further, in step (1), after the conductive glass is cleaned with detergent, deionized water, anhydrous ethanol and deionized water are added in turn and ultrasonic is applied for 5-15 minutes each time.

[0012] Further, in step (2), before spin coating NiO x layer, polyimide adhesive tape is first pasted on the conductive glass and is irradiated under ultraviolet light for 5-15 minutes.

[0013] Further, in step (2), the spin coating of the NiO x layer uses NiO x nanocrystal aqueous solution with a concentration of 15-30 mg / mL, the spin coating speed is 2000-4000 rpm and the time is 30-60 seconds; the spin coating of the PVK layer uses lead methylamine iodine (MAPbI3) solution with a concentration of 1.0-1.2 M, the solvent is DMF and DMSO (volume ratio 2-8:1), the solution is stirred for 2-4 hours at room temperature after being prepared, the spin coating speed is 1000-5000 rpm and the time is 30-60 seconds; the spin coating of the SnO2 layer uses SnO2 nanocrystal solution with a concentration of 0.15-0.3 M, the solvent is ethyl acetate (EA), the spin coating speed is 2000-5000 rpm and the time is 30-60 seconds.

[0014] Further, in step (3), the electrode evaporated is silver electrode, the evaporation current is 40-45 A and the time is 4-5 minutes.

[0015] Working principle: by controlling the spin coating speed and the concentration of precursor solution, the thickness and uniformity of each layer are adjusted. When sunlight is irradiated, the PVK layer will excite hole-electron pairs, the holes are guided into the external circuit through the hole transport layer (HTL layer, i.e. NiO x layer) and the electrons are guided into the external circuit through the electron transport layer (ETL layer, i.e. SnO2 layer), forming a path. Improving the uniformity of each layer is conducive to reducing the probability of hole-electron recombination, so as to prepare a battery with better performance. In addition, SnO2 has oil solubility, which is conducive to improving the waterproof performance of the device.

[0016] Advantages: compared with the prior art, the present application has the following obvious advantages:

[0017] (1) No high-cost equipment such as glove boxes were used in the entire production process. The entire process was prepared in the air, which reduced the production cost and made the operation convenient. Stable perovskite solar cells in the air were successfully prepared.

[0018] (2) NiO x SnO2 and SnO2 are inorganic hole and electron collection and transport layers that are particularly well matched with organic perovskite materials. They are not only stable, non-toxic, and inexpensive, but also have very good charge transport performance.

[0019] (3) This invention uses oil-soluble SnO2 to achieve the direct deposition of SnO2 electron transport layer on perovskite without damaging the perovskite layer, and for the first time prepares an inverted structure all-inorganic transport layer ITO / NiO. x / PVK / SnO2 / Ag perovskite solar cells;

[0020] (4) The thickness of each layer can be adjusted by regulating the concentration of the precursor solution and the spin coating speed to optimize the photoelectric performance of the battery:

[0021] (5) The SnO2 layer used as the top electron transport material is dense and does not absorb ultraviolet light, which improves the waterproof and UV-resistant performance of the entire battery.

[0022] (6) All reagents used are non-toxic or slightly toxic. No highly toxic reagents are used in the entire preparation process. The production process is more environmentally friendly than existing processes. Attached Figure Description

[0023] Figure 1 This is a cross-sectional view of the battery.

[0024] Figure 2 For Example 1, the small area (0.0707 cm²) 2 IU curve of perovskite solar cell device;

[0025] Figure 3 Example 2: Large area (1cm) 2 IU curve of perovskite solar cell device. Detailed Implementation

[0026] The technical solution of the present invention will be further described below with reference to the accompanying drawings.

[0027] Example 1

[0028] Small area (0.0707cm) 2 The fabrication of solar cell devices includes the following steps:

[0029] (1) Clean the ITO conductive glass with size of 20mm x 5mm with detergent, then add deionized water, anhydrous ethanol and deionized water in turn, each for 5 minutes, and dry in a drying oven for standby;

[0030] (2) In air environment, paste the above cleaned and dried ITO glass with 15mm x 5mm polyimide tape, irradiate under ultraviolet light for 5 minutes, then spin-coat NiO x layer, use NiO x nanocrystal aqueous solution with concentration of 25mg / mL, filter with 0.45μm PTFE filter membrane before spin-coating, spin-coating speed is 3000rpm, time is 60s. After spin-coating, heat on a constant temperature table at 130℃ for 30 minutes;

[0031] (3) In ambient air, spin-coat perovskite layer on the NiO x layer of step (2), use 1.2M mixed solution of lead iodide and methylamine iodine, solvent is mixed solvent of DMF and DMSO with volume ratio of 4:1. Spin-coating is divided into two stages, the first stage is 1000rpm for 8 seconds; the second stage is 400 revolutions per minute for 23 seconds. At the last 15 seconds of the second stage program, add 300μL ethyl acetate (EA) as anti-solvent. The obtained sample is annealed in an oven at 100℃ for 15 minutes;

[0032] (4) In ambient air, spin-coat SnO2 layer on the perovskite layer of step (3), use 0.177M SnO2 nanocrystal ethyl acetate solution, spin-coating speed is 3200 revolutions per minute, time is 45 seconds, a total of twice. The obtained sample is annealed in an oven at 80℃ for 15 minutes;

[0033] (5) Transfer the sample obtained in step (4) into an evaporation instrument to evaporate silver electrode, evaporation current is 45A, time is 4 minutes, the mask aperture used is 2mm round hole, to make the whole battery device, the obtained battery cross-sectional structure is as shown in Figure 1 (wherein the silver electrode is not shown). The test light intensity of the battery is a standard sunlight (100mW / cm 2 ), the black mold with light transmission aperture of 0.0707cm 2 or 1cm 2 is used to shield the part of the battery that is not needed for testing, the scanning speed of 10mV / s is used to measure the J-V curve, then the open circuit voltage (V OC ), short circuit current (J SC ), fill factor (FF) and photoelectric conversion efficiency (PCE) of the battery are calculated, the measured J-V curve and efficiency are as shown in Figure 2 , the highest efficiency reaches 20.1%.

[0034] Example 2

[0035] Large area (1 cm 2 ) solar cell device preparation, comprising the following steps:

[0036] (1) Clean the ITO conductive glass of 20 mm x 5 mm size with detergent, then add deionized water, anhydrous ethanol, and deionized water successively, each for 5 minutes, and dry in a drying oven for standby;

[0037] (2) In an air environment, paste the above cleaned and dried ITO glass with a 15 mm x 5 mm polyimide tape, and irradiate it under ultraviolet light for 5 minutes, then spin-coat a NiO x layer using a NiO x nanocrystal aqueous solution with a concentration of 25 mg / mL, filtered with a 0.45 μm PTFE filter membrane before spin-coating, at a spin-coating speed of 3000 rpm for 60 seconds. After spin-coating, heat on a constant temperature table at 130°C for 30 minutes;

[0038] (3) In an ambient air environment, spin-coat a perovskite layer on the NiO x layer of step (2) using a 1.2 M mixed solution of lead iodide and methylamine iodine, with a mixed solvent of DMF and DMSO in a volume ratio of 4:1. Spin-coating is divided into two stages, the first stage at a speed of 1000 rpm for 8 seconds; the second stage at a speed of 4000 rpm per minute for 23 seconds. At the last 15 seconds of the second stage program, add 300 μL of ethyl acetate (EA) as an anti-solvent. The obtained sample is annealed in an oven at 100°C for 15 minutes;

[0039] (4) In an ambient air environment, spin-coat a SnO2 layer on the perovskite layer of step (3) using a 0.177 M SnO2 nanocrystal ethyl acetate solution, at a spin-coating speed of 3200 rpm per minute for 45 seconds, for a total of two times. The obtained sample is annealed in an oven at 80°C for 15 minutes;

[0040] (5) Transfer the sample obtained in step (4) to an evaporation instrument to evaporate a silver electrode, with an evaporation current of 45 A for 4 minutes, using a mask hole of a square hole with a side length of 10 millimeters to make the entire cell device, and the obtained cell cross-sectional structure is as shown in Figure 1 (wherein the silver electrode is not shown). The test light intensity of the cell is a standard sunlight (100 mW / cm 2 ), a black mold with a light transmission aperture of 0.0707 cm 2 or 1 cm 2 is used to block the part of the cell that is not needed for testing, and the J-V curve is measured using a scanning speed of 10 mV / s, and then the open circuit voltage (V OC ), short circuit current (J SC), fill factor (FF) and photoelectric conversion efficiency (PCE) of the cells, the measured J-V curves and efficiencies are shown in Figure 3 Fig. 6, the highest efficiency reaching 14.6%.

Claims

1. A high-efficiency all-inorganic transport layer perovskite solar cell for use in air, characterized in that, Including a glass substrate stacked in sequence, NiO x Layer, PVK layer, SnO2 layer and electrode.

2. The high-efficiency all-inorganic transport layer perovskite solar cell in air according to claim 1, characterized in that, The NiO x The thickness of the layer is 10-30nm, the thickness of the PVK layer is 200-500nm, and the thickness of the SnO2 layer is 10-30nm.

3. A method for preparing a high-efficiency all-inorganic transport layer perovskite solar cell in air as described in claim 1 or 2, characterized in that, Includes the following steps: (1) Clean the ITO conductive glass; (2) NiO x Layers of PVK, SnO2, and PVK are sequentially spin-coated onto ITO conductive glass. (3) Evaporated electrode.

4. The method for preparing a high-efficiency all-inorganic transport layer perovskite solar cell in air according to claim 3, characterized in that, In step (1), after cleaning the conductive glass with dish soap, it is ultrasonically cleaned with deionized water, anhydrous ethanol, and deionized water in sequence for 5-15 minutes each time.

5. The method for preparing a high-efficiency all-inorganic transport layer perovskite solar cell in air according to claim 3, characterized in that, In step (2), NiO is spin-coated x First, attach polyimide tape to the conductive glass and irradiate it under ultraviolet light for 5-15 minutes.

6. The method for preparing a high-efficiency all-inorganic transport layer perovskite solar cell in air according to claim 3, characterized in that, In step (2), spin-coating NiO x The layer uses NiO x The nanocrystal aqueous solution has a concentration of 15-30 mg / mL, a spin coating speed of 2000-4000 rpm, and a spin coating time of 30-60 seconds.

7. The method for preparing a high-efficiency all-inorganic transport layer perovskite solar cell in air according to claim 3, characterized in that, In step (2), the PVK layer is spin-coated with a 1.0-1.2M methylamine lead iodine solution at a spin-coating speed of 1000-5000 rpm for 30-60 seconds.

8. The method for preparing a high-efficiency all-inorganic transport layer perovskite solar cell in air according to claim 7, characterized in that, The solvent in the solution is DMF and DMSO in a volume ratio of 2-8:

1. After the solution is prepared, it is stirred at room temperature for 2-4 hours.

9. The method for preparing a high-efficiency all-inorganic transport layer perovskite solar cell in air according to claim 3, characterized in that, In step (2), the SnO2 layer is spin-coated using a SnO2 nanocrystal solution with a concentration of 0.15-0.30M and ethyl acetate as the solvent. The spin-coating speed is 2000-5000 rpm and the time is 30-60 seconds.

10. The method for preparing a high-efficiency all-inorganic transport layer perovskite solar cell in air according to claim 3, characterized in that, In step (3), the electrode to be vapor-deposited is an Ag electrode, and a current of 40-45A is used for vapor deposition for 4-5 minutes.

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