Metal halide perovskite materials, preparation method thereof as well as solar cell device and preparation method of solar cell device
A technology of metal halide and perovskite materials, which can be used in the preparation of amino compounds, organic compounds, electrical solid-state devices, etc., and can solve problems such as stability and short boards
Active Publication Date: 2019-06-21
SUZHOU UNIV
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AI-Extracted Technical Summary
Problems solved by technology
Although the current maximum efficiency of small-area laboratory-grade perovskite solar cells has exceeded...
Abstract
The invention discloses a preparation method of metal halide perovskite materials. The method comprises steps as follows: a. introducing crown ether materials into a metal halide perovskite pecursor solution; b. treating an obtained solution from step (a) with a solution method to obtain metal halide perovskite materials, wherein the crown ether materials are selected from at least one of crown ether, heteroatomic crown ether and crown ether derivatives. The invention also provides the metal halide perovskite materials prepared with the preparation method as well as a metal halide perovskite solar cell device based on the metal halide perovskite materials and a preparation method of the device. The photovoltaic property and the stability of the solar cell device prepared from the metal halide perovskite materials are improved significantly.
Application Domain
Organic compound preparationSolid-state devices +6
Technology Topic
Perovskite solar cellMetal halides +3
Image
Examples
- Experimental program(4)
Example Embodiment
[0074] Example 1
[0075] The preparation method and specific steps of a typical laboratory-level "n-i-p" type perovskite solar cell device are described. Select mixed ionic lead halide perovskite FA 0.85 MA 0.15 Pb(I 0.85 Br 0.15 ) 3 , its precursor components formamidine iodide (FAI), lead iodide (PbI 2 ), methylamine bromide (MABr), lead bromide (PbBr 2 ) is 1.02:1.05:0.18:0.18, the solvent adopts DMSO:DMF volume ratio as a mixed solvent of 1:4, and the molar concentration of the perovskite precursor solution (calculated as lead element) is 1.2 mol/L, weighed, stirred, dissolved, filtered and set aside. The preparation method of the perovskite solution with crown ether is to weigh or measure the required amount of 15-crown ether-5 and add it to the prepared perovskite solution, stir and dissolve evenly.
[0076] Cleaning of the substrate: The FTO/glass substrate is ultrasonically cleaned for about 20 minutes with detergent/water, deionized water, acetone, and isopropanol in sequence, and then dried in a drying oven or blown dry with nitrogen gas for use.
[0077] Substrate pretreatment: The clean FTO/glass substrate is subjected to UV-ozone or oxygen plasma pretreatment for about 20 minutes.
[0078] Preparation of the electron transport layer: Take an appropriate amount of titanium oxide precursor solution prepared by tetraisopropoxide and isopropanol and spin-coat it on the FTO/glass substrate, then transfer it to a laboratory environment with low humidity outside, heat it at 450 °C On-stage annealing for about 30 minutes to complete the electron transport layer TiO x preparation.
[0079] Preparation of the perovskite light-absorbing layer: in the glove box, take an appropriate amount of the prepared perovskite precursor solution and the perovskite solution introduced with the preferred 10 mmol/L 15-crown ether-5 and spin-coat on the TiO x On the substrate, 10-15 seconds before the end of spin-coating, anti-solvent treatment is performed on the spin-coated film with chlorobenzene, and finally the spin-coated substrate is annealed on a hot stage at ~100°C for about 10 minutes to complete the light absorption of the perovskite film. layer preparation.
[0080]The preparation of the hole transport layer: the hole transport material Spiro-MeOTAD, lithium salt (Li-TFSI), cobalt salt (FK209Co(III) TFSI Salt), 4-tert-butylpyridine (tBP) with a concentration of 1:0.5:0.03:2 for doping treatment, and then take an appropriate amount of the prepared solution and spin-coat it on the perovskite film to complete the preparation of the hole transport layer Spiro-MeOTAD. Then, the device prepared by the above spin coating was transferred to an electronic drying oven for oxidation treatment for about 12 hours.
[0081] Evaporation of metal electrodes: Finally, transfer the oxidized device to a vacuum evaporation coating system in a glove box for evaporation of ~10nm molybdenum trioxide and 100nm metallic silver, and finally complete the preparation of the entire perovskite solar cell device.
[0082] Device testing: The current-voltage test of the device is carried out under a standard simulated sunlight.
[0083] image 3 It is the steady-state fluorescence spectrum of the mixed ion-type perovskite solar cell before and after introducing 10 mmol/L 15-crown-5; Figure 4 is the current-voltage characteristic of the mixed ion type perovskite solar cell before and after introducing 10 mmol/L 15-crown ether-5; Figure 5 It is a diagram of the energy conversion efficiency change of the mixed ion-type perovskite solar cell before and after introducing 10 mmol/L 15-crown ether-5 during the storage stability test of the device for 42 days (ie 1000 hours). The perovskite and solar cell thereof before and after introducing the preferred 10 mmol/L 15-crown ether-5 have the following characteristics:
[0084] (1) Compared with the unintroduced mixed-ionic perovskite, the steady-state fluorescence intensity of the mixed-ionic perovskite introduced with 10 mmol/L 15-crown-5 was significantly improved.
[0085] (2) Compared with the unintroduced mixed ion perovskite solar cell, the photovoltaic performance of the mixed ion perovskite solar cell introduced with 10 mmol/L 15-crown ether-5 was significantly improved, and the energy conversion efficiency was from 18.5% improved to 20.2%.
[0086] (3) Compared with the unintroduced mixed ion type perovskite solar cell, the device stability of the mixed ion type perovskite solar cell introduced with 10 mmol/L 15-crown ether-5 is improved, that is, after about 42 After 1 day (ie 1000 hours) glove box storage stability test, the efficiency decline rate of the perovskite solar cell device was reduced from 30.1% without introduction to 14.8% with the introduction of 10 mmol/L 15-crown-5.
[0087] Table 1 Photovoltaic parameter performance of mixed ion perovskite solar cells before and after introducing 15-crown ether-5
[0088]
Example Embodiment
[0089] Example 2
[0090] The preparation method and specific steps of a typical laboratory-level "n-i-p" type perovskite solar cell device are described. We prefer mixed ionic lead halide perovskite FA 0.85 MA 0.15 Pb(I 0.85 Br 0.15 ) 3 , its precursor components formamidine iodide (FAI), lead iodide (PbI 2 ), methylamine bromide (MABr), lead bromide (PbBr 2 ) is 1.02:1.05:0.18:0.18, the solvent adopts DMSO:DMF volume ratio as a mixed solvent of 1:4, and the molar concentration of the perovskite precursor solution (calculated as lead element) is 1.2 mol/L, weighed, stirred, dissolved, filtered and set aside. The preparation method of the perovskite solution with crown ether is to weigh or measure an appropriate amount of dibenzo-21-crown ether-7 and add it to the prepared perovskite solution, stir and dissolve evenly.
[0091] Cleaning of the substrate: The FTO/glass substrate is ultrasonically cleaned for about 20 minutes with detergent/water, deionized water, acetone, and isopropanol in sequence, and then dried in a drying oven or blown dry with nitrogen gas for use.
[0092] Substrate pretreatment: The clean FTO/glass substrate is subjected to UV-ozone or oxygen plasma pretreatment for about 20 minutes.
[0093] Preparation of the electron transport layer: Take an appropriate amount of titanium oxide precursor solution prepared by tetraisopropoxide and isopropanol and spin-coat it on the FTO/glass substrate, then transfer it to a laboratory environment with low humidity outside, heat it at 450 °C On-stage annealing for about 30 minutes to complete the electron transport layer TiO x preparation.
[0094] Preparation of the perovskite light-absorbing layer: in the glove box, take an appropriate amount of the prepared perovskite precursor solution and spin-coat the perovskite solution introducing the preferred 2.5 mmol/L dibenzo-21-crown-7 in TiO x On the substrate, 10-15 seconds before the end of spin-coating, anti-solvent treatment is performed on the spin-coated film with chlorobenzene, and finally the spin-coated substrate is annealed on a hot stage at ~100°C for about 10 minutes to complete the light absorption of the perovskite film. layer preparation.
[0095] The preparation of the hole transport layer: the hole transport material Spiro-MeOTAD, lithium salt (Li-TFSI), cobalt salt (FK209Co(III) TFSI Salt), 4-tert-butylpyridine (tBP) with a concentration of 1:0.5:0.03:2 for doping treatment, and then take an appropriate amount of the prepared solution and spin-coat it on the perovskite film to complete the preparation of the hole transport layer Spiro-MeOTAD. Then, the device prepared by the above spin coating was transferred to an electronic drying oven for oxidation treatment for about 12 hours.
[0096] Evaporation of metal electrodes: Finally, transfer the oxidized device to a vacuum evaporation coating system in a glove box for evaporation of ~10nm molybdenum trioxide and 100nm metallic silver, and finally complete the preparation of the entire perovskite solar cell device.
[0097] Device testing: The current-voltage test of the device is carried out under a standard simulated sunlight.
[0098] Image 6 is the current-voltage characteristic of a mixed-ion perovskite solar cell introduced with 2.5 mmol/L dibenzo-21-crown ether-7. The perovskite and its solar cell before and after introducing the preferred 2.5 mmol/L dibenzo-21-crown ether-7 have the following characteristics:
[0099] (1) Compared with the unintroduced mixed ion perovskite solar cell, the photovoltaic performance of the mixed ion perovskite solar cell introduced with 2.5 mmol/L dibenzo-21-crown-7 was significantly improved, Energy conversion efficiency increased from 18.5% to 19.6%.
Example Embodiment
[0100] Example 3
[0101] The preparation method and specific steps of a typical laboratory-level "n-i-p" type inorganic perovskite solar cell device are described. Select the inorganic lead halide perovskite CsPbI 2 Br, its precursor components cesium iodide (CsI), lead iodide (PbI 2 ), lead bromide (PbBr 2 The molar ratio of substances between ) is 1:0.5:0.5, the solvent adopts DMF:DMSO volume ratio as a mixed solvent of 1:4, and the molar concentration of the inorganic perovskite precursor solution (calculated by lead element) is 0.7 moles /L, weighed, stirred, dissolved, filtered, and set aside. The method for preparing the inorganic perovskite solution with crown ether is to weigh or measure an appropriate amount of 18-crown ether-6 and add it to the prepared inorganic perovskite solution, stir and dissolve evenly.
[0102] Cleaning of the substrate: The FTO/glass substrate is ultrasonically cleaned for about 20 minutes with detergent/water, deionized water, acetone, and isopropanol in sequence, and then dried in a drying oven or blown dry with nitrogen gas for use.
[0103] Substrate pretreatment: The clean FTO/glass substrate is subjected to UV-ozone or oxygen plasma pretreatment for about 20 minutes.
[0104] Preparation of the electron transport layer: Take an appropriate amount of titanium oxide precursor solution prepared by tetraisopropoxide and isopropanol and spin-coat it on the FTO/glass substrate, then transfer it to a laboratory environment with low humidity outside, heat it at 450 °C On-stage annealing for about 30 minutes to complete the electron transport layer TiO x preparation.
[0105] Preparation of the perovskite light-absorbing layer: In a glove box, take an appropriate amount of the prepared inorganic perovskite precursor solution and the inorganic perovskite solution introduced with the preferred 5 mmol/L 18-crown-6 and spin-coat on TiO x On the substrate, 10-15 seconds before the end of spin-coating, anti-solvent treatment is performed on the spin-coated film with chlorobenzene, and finally the spin-coated substrate is annealed on a hot stage at ~275°C for about 10 minutes to complete the inorganic perovskite film Preparation of light absorbing layer.
[0106] Preparation of the hole transport layer: Spin-coat an appropriate amount of prepared P3HT (15 mg/ml, dissolved in chlorobenzene) solution on the perovskite film, and anneal on a hot stage at 100°C for about 10 minutes to complete the hole transport Preparation of layer P3HT.
[0107] Evaporation of metal electrodes: Finally, transfer the oxidized device to a vacuum evaporation coating system in a glove box for evaporation of ~10nm molybdenum trioxide and 100nm metallic silver, and finally complete the preparation of the entire inorganic perovskite solar cell device.
[0108] Device testing: The current-voltage test of the device is carried out under a standard simulated sunlight.
[0109] Figure 7 is the steady-state fluorescence spectrum of the inorganic perovskite solar cell before and after introducing 5 mmol/L 18-crown-6; Figure 8 is the current-voltage characteristic of the inorganic perovskite solar cell before and after introducing 5 mmol/L 18-crown ether-6; Figure 9 is the device stability performance of inorganic perovskite solar cells before and after introducing 10, 20, 40 mmol/L 18-crown ether-6 (after testing in air). The perovskite and solar cell thereof before and after introducing the preferred 5 mmol/L 18-crown ether-6 have the following characteristics:
[0110] (1) Compared with the unintroduced inorganic perovskite, the steady-state fluorescence intensity of the inorganic perovskite introduced with 5 mmol/L 18-crown ether-6 was significantly improved.
[0111] (2) Compared with the unintroduced inorganic perovskite solar cells, the photovoltaic performance of the inorganic perovskite solar cells introduced with 5 mmol/L 18-crown ether-6 was significantly improved, and the energy conversion efficiency increased from 6.43% to 7.11% %.
[0112] (3) Compared with the unintroduced inorganic perovskite solar cells, after the current-voltage test (in the air), the inorganic perovskite undergoes serious phase transition or degradation, and the introduction of 10, 20, 40 mmol/L 18-crown The device stability of ether-6 based inorganic perovskite solar cells is continuously enhanced.
[0113] Table 2 Photovoltaic parameter performance of inorganic perovskite solar cells before and after introducing 18-crown ether-6
[0114]
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