CN108054280B - Solar cell - Google Patents
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- CN108054280B CN108054280B CN201810040565.0A CN201810040565A CN108054280B CN 108054280 B CN108054280 B CN 108054280B CN 201810040565 A CN201810040565 A CN 201810040565A CN 108054280 B CN108054280 B CN 108054280B
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Abstract
The invention provides a solar cell, which comprises a light absorption layer, wherein the light absorption layer is made of photovoltaic materials. According to the invention, the surface of the perovskite material is coated with the nano tin dioxide film, so that the failure of the battery caused by the decomposition of the perovskite material by moisture in the air can be effectively avoided, and the water resistance and the stability of the perovskite material are enhanced. Meanwhile, the nano tin dioxide film can also enhance the light absorption of the perovskite material and improve the photoelectric conversion efficiency of the perovskite material. The water-resistant perovskite photovoltaic material provided by the invention is used for assembling the solar cell, so that the photoelectric conversion efficiency of the solar cell can reach 12.8% at most.
Description
The application is a divisional application of patents with application numbers of 201510965745.6, 2015, 12, and 22, and entitled "a water-resistant perovskite photovoltaic material and a preparation method thereof".
Technical Field
The invention relates to the technical field of photovoltaic materials, in particular to a water-resistant perovskite photovoltaic material and a preparation method thereof.
Background
The consumption of traditional fossil fuels has great influence on the environment, so that the demand of clean energy is gradually increased, and solar energy has great application value as clean energy, so that the development of a solar photovoltaic material with high photoelectric conversion efficiency, stable performance and long service life has great significance. The traditional inorganic semiconductor solar cell has the problems of high cost, high pollution and the like, and the search for a novel solar cell is still a hot spot of current research.
The perovskite type organic metal halide material has excellent photoelectric property and is easy to synthesize, and has been widely used in solar cell research, the maximum energy conversion efficiency of the current solar cell based on the material reaches 19%, the theoretical conversion efficiency can reach 50%, and the perovskite type organic metal halide material has great development potential.
The perovskite structure material mainly serves as a light absorption layer in the solar cell, and the perovskite photovoltaic material has the characteristics of high carrier mobility, adjustable band gap, solution method preparation, high absorption coefficient and the like, so that the solar cell made of the perovskite photovoltaic material has high photoelectric conversion efficiency.
The Chinese invention patent application publication specification CN201410340552 discloses a perovskite solar cell and a preparation method thereof, wherein a TiO 2/perovskite structure material is adopted as a light absorption layer of the cell, and a spiro-OMeTAD is adopted as a hole transmission layer, so that the energy conversion rate of the prepared solar cell is 11.2-12.6%. It has been studied that the photoelectric conversion rate of the assembled solar cell is 10.9% by using Al2O3 nano-material as a perovskite absorption layer bracket (LeeMM, Teuscher J, SnaithHJ, et. EffectingHybridsorangiscells based on mesoporous-superstructured solar cells. science, 2012, 338: 643-647.). The invention discloses a perovskite structure solar cell and a preparation method thereof in Chinese invention patent application publication specification CN201310650505.8, wherein a layer of titanium oxide or zinc oxide n-type layer is deposited on fluorine-doped SnO2(FTO) conductive glass, then a layer of hybrid perovskite structure CH3NH3PbI3 is deposited, then a p-type silicon film is deposited, a metal electrode layer is deposited at last, and the photoelectric conversion rate of the solar cell obtained by final assembly can reach 7.53%.
The prior art has the following defects: the perovskite photovoltaic material is poor in chemical stability, prone to be decomposed by water in the air to cause battery failure, sensitive to oxygen in the air, capable of causing performance reduction of the battery, capable of further influencing service life and stability of devices, capable of causing difficulty and cost increase of device packaging, and the perovskite photovoltaic material is a main obstacle to practicability. Therefore, the present inventors have completed the present invention through a large number of studies based on a summary of the prior art.
Disclosure of Invention
The invention is provided aiming at the defects in the prior art, and the technical problem to be solved is to provide a water-resistant perovskite photovoltaic material, wherein the surface of the perovskite material is coated with a nano tin dioxide film, so that the failure of a battery caused by the decomposition of the perovskite material by moisture in the air can be effectively avoided, and the water resistance and the stability of the perovskite material are enhanced. Further provides a preparation method of the water-resistant perovskite photovoltaic material. The water-resistant perovskite photovoltaic material prepared by the method can stabilize the performance of the solar cell and prolong the service life, and the packaging requirement of the device is simplified.
The technical scheme of the invention is as follows:
the invention is realized by the following technical scheme.
The invention relates to a water-resistant perovskite photovoltaic material.
The water-resistant perovskite photovoltaic material is used as an absorption layer in a perovskite solar cell, the support structure is nano TiO2, the perovskite structure material is a material with a chemical formula ABX3, wherein A represents methylamine; b represents Pb; x is one or two halogen elements selected from iodine, bromine or chlorine, and the surface of the perovskite material is coated with a nano tin dioxide film.
The invention relates to a preparation method of a water-resistant perovskite photovoltaic material.
The preparation method of the water-resistant perovskite photovoltaic material comprises the following steps:
(1) preparation of a dense layer of TiO2
Printing a TiO2 thin film layer on FTO glass by a screen printing method, and heating for 30min at 450 ℃ to obtain a dense layer with the thickness of 50 nm;
(2) preparation of a mesoporous layer of TiO2
Mixing nano TiO2 and ethanol according to a weight ratio of 1: 2-5, preparing slurry, spin-coating the dense layer obtained in the step (1), drying at 100-200 ℃, transferring the dense layer to a muffle furnace, and annealing at 300-600 ℃ for 30-60 min to obtain a nano TiO2 mesoporous layer attached to the dense layer;
(3) preparation of perovskite photovoltaic material
Spin-coating a nano TiO2 mesoporous layer obtained in the step (2) with a lead iodide, lead chloride or lead bromide solution with a concentration of 0.8-1.2 mol/L, soaking in isopropanol with a concentration of 8-12 mg/ml CH3NH3I for 15-20 min, washing with isopropanol, heating at 90-110 ℃ for 30-50 min to generate a perovskite structure material of CH3NH3PbI3, CH3NH3PbCl2I or CH3NH3PbBr 2I: thus obtaining the nano TiO2 perovskite photovoltaic material with the thickness of 500-650 nm;
(4) preparation of water-resistant perovskite photovoltaic material
Preparing a tin tetrachloride solution with the concentration of 0.1-1 mg/ml, stirring, dropwise adding 1-3 mg/ml ammonia water solution and a small amount of sol forming aid to enable the pH value of the solution to be 7, forming sol, standing at a constant temperature of 30-50 ℃ to obtain gel sol, spin-coating the prepared gel solution on the nano TiO2 perovskite photovoltaic material prepared in the step (2), drying at the temperature of 90-110 ℃, transferring to a muffle furnace, and annealing at the temperature of 300-600 ℃ for 30-60 min to finally obtain the water-resistant perovskite photovoltaic material with the surface covered with tin dioxide.
The invention provides a water-resistant perovskite photovoltaic material and a preparation method thereof for the first time, and the water-resistant perovskite photovoltaic material has the outstanding characteristics and beneficial effects that:
the invention provides a water-resistant perovskite photovoltaic material for a solar cell, which is used as a light absorption layer in the solar cell. According to the invention, the surface of the perovskite material is coated with the nano tin dioxide film, so that the failure of the battery caused by the decomposition of the perovskite material by moisture in the air can be effectively avoided, and the water resistance and the stability of the perovskite material are enhanced. Meanwhile, the nano tin dioxide film can also enhance the light absorption of the perovskite material and improve the photoelectric conversion efficiency of the perovskite material.
The water-resistant perovskite photovoltaic material provided by the invention is used for assembling the solar cell, so that the photoelectric conversion efficiency of the solar cell can reach 12.8% at most.
Detailed Description
The present invention is described in further detail below with reference to specific embodiments, but the scope of the present invention should not be construed as being limited to the following examples.
Example 1
(1) Preparation of a dense layer of TiO2
Printing a TiO2 thin film layer on FTO glass by a screen printing method, and heating for 30min at 450 ℃ to obtain a dense layer with the thickness of 50 nm;
(2) preparation of a mesoporous layer of TiO2
Mixing nano TiO2 and ethanol according to a weight ratio of 1: 3, preparing slurry, spin-coating the dense layer obtained in the step (1), drying at 110 ℃, transferring the dense layer to a muffle furnace, and annealing at 450 ℃ for 50min to obtain a nano TiO2 mesoporous layer attached to the dense layer;
(3) preparation of perovskite photovoltaic material
Spin-coating a lead iodide, lead chloride or lead bromide solution with the concentration of 0.8mol/L on the nano mica mesoporous layer obtained in the step (3), soaking the nano mica mesoporous layer in isopropanol with the concentration of 10mg/ml CH3NH3I for 15min, washing the nano mica mesoporous layer with the isopropanol, and heating the nano mica mesoporous layer at the temperature of 90 ℃ for 30min to generate a perovskite structure material of CH3NH3PbI3, CH3NH3PbCl2I or CH3NH3PbBr 2I: thus obtaining the nano mica mesoporous/perovskite photovoltaic material with the thickness of 500 nm;
(4) preparation of water-resistant perovskite photovoltaic material
Preparing 0.8mg/ml stannic chloride solution, stirring, dropwise adding 2mg/ml ammonia water solution and a small amount of sol forming auxiliary agent to make the pH value of the solution be 7 to form sol, and standing at constant temperature of 40 ℃ to obtain gel sol. And (3) spin-coating the prepared gel solution on the nano TiO2 perovskite photovoltaic material prepared in the step (2), drying at the temperature of 110 ℃, transferring to a muffle furnace, and annealing at the temperature of 300 ℃ for 50min to finally obtain the water-resistant perovskite photovoltaic material with the surface covered with tin dioxide.
When the perovskite-mica photovoltaic material prepared in the embodiment is used for assembling a solar cell, the photoelectric conversion rate of the cell is 12.7%.
Example 2
The step (1) is the same as the above;
(2) preparation of a mesoporous layer of TiO2
Mixing nano TiO2 and ethanol according to a weight ratio of 1: 2, preparing slurry, spin-coating the slurry to the compact layer obtained in the step (1), drying at 100 ℃, and then transferring the dried compact layer to a muffle furnace to perform annealing treatment 30 at the temperature of 300 ℃ to obtain a nano TiO2 mesoporous layer attached to the compact layer;
(3) preparation of perovskite photovoltaic material
Spin-coating a nano TiO2 mesoporous layer obtained in the step (2) with a lead iodide, lead chloride or lead bromide solution with the concentration of 0.8mol/L, soaking the nano TiO2 mesoporous layer in isopropanol with the concentration of 8mg/ml CH3NH3I for 15min, washing the nano TiO2 mesoporous layer with the isopropanol, and heating the nano TiO2 mesoporous layer at the temperature of 90 ℃ for 50min to generate a perovskite structure material of CH3NH3PbI3, CH3NH3PbCl2I or CH3NH3PbBr 2I: thus obtaining the nano TiO2 perovskite photovoltaic material with the thickness of 500 nm;
(4) preparation of water-resistant perovskite photovoltaic material
Preparing 0.1mg/ml stannic chloride solution, stirring, dropwise adding 1mg/ml ammonia water solution and a small amount of sol forming auxiliary agent to make the pH value of the solution be 7 to form sol, and standing at constant temperature of 30 ℃ to obtain gel sol. And (3) spin-coating the prepared gel solution on the nano TiO2 perovskite photovoltaic material prepared in the step (2), drying at the temperature of 110 ℃, transferring to a muffle furnace, and annealing at the temperature of 600 ℃ for 30min to finally obtain the water-resistant perovskite photovoltaic material with the surface covered with tin dioxide.
When the perovskite-mica photovoltaic material prepared in the embodiment is used for assembling a solar cell, the photoelectric conversion rate of the cell is 11.6%.
Example 3
The step (1) is the same as the above;
(2) preparation of a mesoporous layer of TiO2
Mixing nano TiO2 and ethanol according to a weight ratio of 1: 5, preparing slurry, spin-coating the dense layer obtained in the step (1), drying at 200 ℃, transferring the dense layer to a muffle furnace, and annealing at 600 ℃ for 60min to obtain a nano TiO2 mesoporous layer attached to the dense layer;
(3) preparation of perovskite photovoltaic material
Spin-coating a nano TiO2 mesoporous layer obtained in the step (2) with a lead iodide, lead chloride or lead bromide solution with the concentration of 1.0mol/L, soaking in isopropanol with the concentration of 12mg/ml CH3NH3I for 20min, washing with the isopropanol, and heating at 90 ℃ for 50min to generate a perovskite structure material of CH3NH3PbI3, CH3NH3PbCl2I or CH3NH3PbBr 2I: thus obtaining the nano TiO2 perovskite photovoltaic material with the thickness of 550 nm;
(4) preparation of water-resistant perovskite photovoltaic material
Preparing 1mg/ml stannic chloride solution, stirring, dropwise adding 3mg/ml ammonia water solution and a small amount of sol forming auxiliary agent to make the pH value of the solution be 7 to form sol, and standing at constant temperature of 50 ℃ to obtain gel sol. And (3) spin-coating the prepared gel solution on the nano TiO2 perovskite photovoltaic material prepared in the step (2), drying at the temperature of 90 ℃, transferring the material into a muffle furnace, and annealing at the temperature of 400 ℃ for 30min to finally obtain the water-resistant perovskite photovoltaic material with the surface covered with tin dioxide.
When the perovskite-mica photovoltaic material prepared in the embodiment is used for assembling a solar cell, the photoelectric conversion rate of the cell is 10.8%.
Example 4
The step (1) is the same as the above;
(2) preparation of a mesoporous layer of TiO2
Mixing nano TiO2 and ethanol according to a weight ratio of 1: 3, preparing slurry, spin-coating the dense layer obtained in the step (1), drying at 150 ℃, transferring the dense layer to a muffle furnace, and annealing at 400 ℃ for 50min to obtain a nano TiO2 mesoporous layer attached to the dense layer;
(3) preparation of perovskite photovoltaic material
Spin-coating a nano TiO2 mesoporous layer obtained in the step (2) with a lead iodide, lead chloride or lead bromide solution with the concentration of 1.0mol/L, soaking the nano TiO2 mesoporous layer in isopropanol with the concentration of 10mg/ml CH3NH3I for 15min, washing the nano TiO2 mesoporous layer with the isopropanol, and heating the nano TiO2 mesoporous layer at the temperature of 110 ℃ for 50min to generate a perovskite structure material of CH3NH3PbI3, CH3NH3PbCl2I or CH3NH3PbBr 2I: thus obtaining the 600 nm-thick nano TiO2 perovskite photovoltaic material;
(4) preparation of water-resistant perovskite photovoltaic material
Preparing 0.5mg/ml stannic chloride solution, stirring, dropwise adding 2mg/ml ammonia water solution and a small amount of sol forming auxiliary agent to make the pH value of the solution be 7 to form sol, and standing at constant temperature of 50 ℃ to obtain gel sol. And (3) spin-coating the prepared gel solution on the nano TiO2 perovskite photovoltaic material prepared in the step (2), drying at the temperature of 90 ℃, transferring to a muffle furnace, and annealing at the temperature of 600 ℃ for 50min to finally obtain the water-resistant perovskite photovoltaic material with the surface covered with tin dioxide.
When the perovskite-mica photovoltaic material prepared in the embodiment is used for assembling a solar cell, the photoelectric conversion rate of the cell is 12.8%.
Example 5
The step (1) is the same as the above;
(2) preparation of a mesoporous layer of TiO2
Mixing nano TiO2 and ethanol according to a weight ratio of 1: 3.5 preparing slurry, spin-coating the dense layer obtained in the step (1), drying at 200 ℃, transferring the dense layer to a muffle furnace, and annealing at 600 ℃ for 50min to obtain a nano TiO2 mesoporous layer attached to the dense layer;
(3) preparation of perovskite photovoltaic material
Spin-coating a nano TiO2 mesoporous layer obtained in the step (2) with a lead iodide, lead chloride or lead bromide solution with the concentration of 1.2mol/L, soaking in isopropanol with the concentration of 12mg/ml CH3NH3I for 0min, washing with the isopropanol, and heating at 110 ℃ for 50min to generate a perovskite structure material of CH3NH3PbI3, CH3NH3PbCl2I or CH3NH3PbBr 2I: thus obtaining the nano TiO2 perovskite photovoltaic material with the thickness of 650 nm;
(4) preparation of water-resistant perovskite photovoltaic material
Preparing 0.8mg/ml stannic chloride solution, stirring, dropwise adding 3mg/ml ammonia water solution and a small amount of sol forming auxiliary agent to make the pH value of the solution be 7 to form sol, and standing at constant temperature of 40 ℃ to obtain gel sol. And (3) spin-coating the prepared gel solution on the nano TiO2 perovskite photovoltaic material prepared in the step (2), drying at the temperature of 100 ℃, transferring to a muffle furnace, and annealing at the temperature of 600 ℃ for 60min to finally obtain the water-resistant perovskite photovoltaic material with the surface covered with tin dioxide.
When the perovskite-mica photovoltaic material prepared in the embodiment is used for assembling a solar cell, the photoelectric conversion rate of the cell is 11.9%.
Example 6
The step (1) is the same as the above;
(2) preparation of a mesoporous layer of TiO2
Mixing nano TiO2 and ethanol according to a weight ratio of 1: 4, preparing slurry, spin-coating the dense layer obtained in the step (1), drying at 180 ℃, transferring the dense layer to a muffle furnace, and annealing for 40min at 450 ℃ to obtain a nano TiO2 mesoporous layer attached to the dense layer;
(3) preparation of perovskite photovoltaic material
Spin-coating a nano TiO2 mesoporous layer obtained in the step (2) with a lead iodide, lead chloride or lead bromide solution with the concentration of 1.0mol/L, soaking the nano TiO2 mesoporous layer in isopropanol with the concentration of 10mg/ml CH3NH3I for 20min, washing the nano TiO2 mesoporous layer with the isopropanol, and heating the nano TiO2 mesoporous layer at the temperature of 110 ℃ for 30min to generate a perovskite structure material of CH3NH3PbI3, CH3NH3PbCl2I or CH3NH3PbBr 2I: thus obtaining the 600 nm-thick nano TiO2 perovskite photovoltaic material;
(4) preparation of water-resistant perovskite photovoltaic material
Preparing 0.5mg/ml stannic chloride solution, stirring, dropwise adding 2mg/ml ammonia water solution and a small amount of sol forming auxiliary agent to make the pH value of the solution be 7 to form sol, and standing at constant temperature of 40 ℃ to obtain gel sol. And (3) spin-coating the prepared gel solution on the nano TiO2 perovskite photovoltaic material prepared in the step (2), drying at the temperature of 100 ℃, transferring to a muffle furnace, and annealing at the temperature of 600 ℃ for 60min to finally obtain the water-resistant perovskite photovoltaic material with the surface covered with tin dioxide.
When the perovskite-mica photovoltaic material prepared in the embodiment is used for assembling a solar cell, the photoelectric conversion rate of the cell is 12.1%.
Claims (4)
1. A solar cell comprises a light absorption layer, and is characterized in that the light absorption layer is made of a perovskite photovoltaic material, wherein the surface of the perovskite photovoltaic material is coated with a nano tin dioxide film;
the preparation method comprises the following steps:
(1) preparation of TiO2Dense layer
Printing a TiO2 thin film layer on FTO glass by a screen printing method, and heating for 30min at 450 ℃ to obtain a dense layer with the thickness of 50 nm;
(2) preparation of TiO2Mesoporous layer
Mixing nanometer TiO2And ethanol according to a weight ratio of 1: 2-5, preparing slurry, spin-coating the slurry to the compact layer obtained in the step (1), drying at 100-200 ℃, and transferring the dried compact layer to a muffle furnace at the temperature of 30 DEG CAnnealing treatment is carried out for 30-60 min at the temperature of 0-600 ℃ to obtain the nano TiO attached on the compact layer2A mesoporous layer;
(3) preparation of perovskite structural material
Nano TiO obtained in the step (2)2Spin-coating a mesoporous layer with a lead iodide, lead chloride or lead bromide solution with the concentration of 0.8-1.2 mol/L, soaking in isopropanol with the concentration of 8-12 mg/ml CH3NH3I for 15-20 min, washing with the isopropanol, and heating at 90-110 ℃ for 30-50 min to generate CH3NH3PbI3、CH3NH3PbCl2I or CH3NH3PbBr2I perovskite structure material: thus obtaining the nano TiO with the thickness of 500-650nm2A mesoporous layer perovskite structure material;
(4) preparation of perovskite photovoltaic material
Preparing 0.1-1 mg/ml stannic chloride solution, stirring, dropwise adding 1-3 mg/ml ammonia water solution and a small amount of sol forming aid to enable the pH value of the solution to be 7 to form sol, standing at constant temperature of 30-50 ℃ to obtain gel sol, and spin-coating the prepared gel solution to the nano TiO prepared in the step (3)2Drying the mesoporous layer perovskite structure material at the temperature of 90-110 ℃, transferring the material into a muffle furnace, and annealing the material at the temperature of 300-600 ℃ for 30-60 min to finally obtain a perovskite photovoltaic material with the surface covered with tin dioxide;
the perovskite photovoltaic material is used for assembling the solar cell;
in the step (3), lead iodide, lead chloride or lead bromide is reacted with CH3NH3Respectively dissolving the I into gamma-butyrolactone according to the molar ratio of 1:1, and then stirring and reacting at the temperature of 55-65 ℃ to obtain methylamine lead iodine, methylamine lead iodine chlorine or methylamine lead iodine bromine solution.
2. The solar cell according to claim 1, wherein the thickness of the perovskite structure material with the surface coated with nano tin dioxide is 500-650 nm.
3. The solar cell according to claim 1, wherein the thickness of the nano tin dioxide covered by the perovskite structure material is 50-100 nm.
4. The solar cell according to claim 1, wherein the perovskite structure material is a material of formula ABX3, wherein a represents methylamine; b represents Pb; x is one or two halogen elements selected from iodine, bromine or chlorine.
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| CN106784338A (en) * | 2016-11-21 | 2017-05-31 | 天津市职业大学 | A kind of Ca-Ti ore type opto-electronic conversion composite sol and preparation method thereof |
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| CN108054280A (en) | 2018-05-18 |
| CN105489765A (en) | 2016-04-13 |
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