CN113629192A - Dye-sensitized and double-perovskite hybrid solar cell and preparation method thereof - Google Patents
Dye-sensitized and double-perovskite hybrid solar cell and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a dye-sensitized and double-perovskite hybrid solar cell and a preparation method thereof, belonging to the technical field of perovskite solar cells. Solves the problem that the prior non-lead double perovskite material is caused by Cs2AgBiBr6The wider optical band gap leads to poorer optical absorption capability and low photocurrent, thereby leading to the technical problem of lower efficiency of the device. The hybrid solar cell comprises a transparent conductive glass cathode, an electron transport layer, a perovskite layer, a hole transport layer and a metal anode from bottom to top in sequence; the electron transport layer is titanium dioxide TiO sensitized by indole dyes D102, D131 or D1492(ii) a The perovskite layer is Cs2AgBiBr6. The indole dye simultaneously contributes to the optical absorption and photocurrent of the device as a photosensitive material. The preparation method provided by the inventionCompared with the device prepared by taking common titanium dioxide as an electron transport material, the device prepared by the method has the advantages that the photocurrent is obviously improved, the highest photoelectric conversion efficiency reaches 4.23 percent, and the device is a non-lead double perovskite solar cell with the highest efficiency.
Description
Technical Field
The invention belongs to the technical field of perovskite solar cells, and particularly relates to a titanium dioxide film sensitized by any one of three indole dyes D102, D131 and D149 as an electron transport layer and based on Cs2AgBi Br6A dye-sensitized and double-perovskite hybrid solar cell used as a perovskite light absorption layer and a preparation method thereof.
Background
Perovskite solar cells have now achieved comparable energy conversion efficiencies and lower fabrication costs to silicon-based solar cells. However, the conventional lead-based perovskite solar cell is difficult to be applied on a large scale due to the existence of lead in the material, poor stability and the like. The double perovskite is an important component of the non-lead perovskite material, the solar cell prepared by the material can obtain good energy conversion efficiency while ensuring the stability, and the double perovskite material which is researched most at present and has the best photovoltaic performance is Cs2AgBiBr6. However, the material has a wide band gap and poor light absorption capability, and the photoelectric performance of the material is limited.
Disclosure of Invention
The invention aims to solve the problem that the prior art is not lead double perovskite material due to Cs2AgBiBr6The wide optical band gap leads to poor optical absorption capacity and low photocurrent, thereby leading to the technical problem of low device efficiency, and provides a titanium dioxide film sensitized by any one of three indole dyes D102, D131 and D149 as an electron transport layer and based on Cs2AgBiBr6A dye-sensitized and double-perovskite hybrid solar cell used as a perovskite light absorption layer and a preparation method thereof.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the invention provides a dye-sensitized and double-perovskite hybrid solar cell which sequentially comprises a transparent conductive glass cathode, an electron transport layer, a perovskite layer, a hole transport layer and a metal anode from bottom to top;
it is characterized in that the preparation method is characterized in that,
the electron transport layer is dye-sensitized titanium dioxide, specifically indole dye D102, D131 or D149-sensitized titanium dioxide;
the structural formula of the indole dye D102, D131 or D149 is as follows:
the perovskite layer is Cs2AgBiBr6。
In the technical scheme, the cathode of the transparent conductive glass is fluorine-doped indium tin oxide (FTO).
In the technical scheme, the electron transport layer structure is c-TiO2/m-TiO2D102, D131 or D149.
In the above technical solution, the hole transport layer is 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-OMeTAD).
In the above technical solution, the metal anode is Ag.
In the technical scheme, the thickness of the electron transport layer is 470nm, the thickness of the perovskite layer is 210nm, the thickness of the hole transport layer is 70nm, and the thickness of the metal anode is 60 nm.
The invention also provides a preparation method of the hybrid solar cell of dye sensitization and double perovskites, which comprises the following steps:
1) and (3) treating a transparent conductive glass cathode:
carrying out ultraviolet ozone pretreatment on the cleaned transparent conductive glass;
2) preparing and processing an electron transport layer:
placing the transparent conductive glass pretreated by ultraviolet ozone in the step 1) in a spin coater, spin-coating isopropyl titanate solution, immediately placing in a muffle furnace for annealing treatment,placing the titanium dioxide nano particle colloid solution in a spin coater again after annealing is finished, randomly placing the titanium dioxide nano particle colloid solution in a muffle furnace for annealing treatment, and placing TiCl after annealing is finished4Finally, dipping the obtained product in acetonitrile and tert-butyl alcohol solution of indole dye to prepare an electron transport layer;
the indole dye is D102, D131 or D149;
3) preparation of perovskite layer:
subjecting perovskite precursor Cs2AgBiBr6The solution is placed on a hot bench for magnetic stirring, and after the solution is cooled to room temperature, the perovskite precursor Cs is added2AgBiBr6Filtering the solution through a filter membrane; then putting the device in the step 2) into a glove box filled with nitrogen, and spin-coating the perovskite precursor Cs on the electron transport layer2Placing the AgBiBr solution on a hot table for annealing treatment after the spin coating is finished, and preparing a perovskite layer;
4) preparation of hole transport layer:
spin coating on the perovskite layer to prepare a hole transport layer;
5) preparing a metal anode:
and evaporating a metal anode on the hole transport layer by using a vacuum evaporation coating machine.
In the above technical solution, a specific embodiment of the method for preparing the hybrid solar cell of dye-sensitized and double perovskite is as follows:
1) and (3) treating a transparent conductive glass cathode:
carrying out ultraviolet ozone pretreatment on the cleaned transparent conductive glass for 20 minutes;
2) preparing and processing an electron transport layer:
placing the transparent conductive glass pretreated by ultraviolet ozone in the step 1) in a spin coater, spin-coating isopropyl titanate solution, rotating at 4000rpm for 30s, and then placing in a muffle furnace for annealing at 500 ℃ for 30 min; after the substrate is cooled, spin-coating titanium dioxide nano particle colloidal solution on the substrate, rotating at 2000rpm for 30s, and annealing at 500 ℃ for 30 minutes; after annealing, it is placed inTiCl4In the solution, the temperature and the time are kept at 70 ℃ for 1h, and the annealing temperature and the annealing time are kept at 500 ℃ for 30 minutes; and after the annealing is finished, soaking the indole dye into acetonitrile and tert-butyl alcohol (volume ratio is 1: 1) solution of the indole dye, wherein the concentration of the solution is 0.3mg/mL, and the volume ratio of the acetonitrile to the tert-butyl alcohol is 1: 1;
3) preparation of perovskite layer:
subjecting perovskite precursor Cs2AgBiBr6The solution is placed on a hot bench at 100 ℃ and stirred for 2 hours by magnetic force, and after the solution is cooled to room temperature, the perovskite precursor Cs is added2AgBiBr6Filtering the solution through a 20-micron filter membrane; putting the device in the step 2) into a glove box filled with nitrogen, and spin-coating a perovskite precursor Cs on the electron transport layer2AgBiBr6The spin coating speed of the solution is 2000rpm, the time is 60 seconds, the solution is placed on a hot bench for annealing treatment after the spin coating is finished, and the annealing temperature and the annealing time are 200 ℃ for annealing for 10 minutes;
4) preparation of hole transport layer:
dissolving Spiro-OMeTAD in chloroform solution at a concentration of 80mg/mL, adding 10.5. mu.L of 4-tert-butylpyridine (TBP) and 46.5. mu.L of Li-TFSI solution dissolved in acetonitrile solution at a concentration of 170mg/mL, and after sufficient magnetic stirring, spin-coating Spiro-OMeTAD solution on the perovskite layer at a rotation speed of 4000rpm for 30 seconds;
5) preparing a metal anode:
using vacuum evaporation coating machine to make pressure less than 6 x 10-4Evaporating metal anode on the hole transport layer at Pa with the evaporation rate of
In the above technical scheme, the perovskite layer precursor Cs2AgBiBr6The preparation process of the solution is as follows:
in a nitrogen glove box, 0.5mMol of BiBr3224.3mg and 0.5mMol of AgBr93.9mg and 1mMol of CsBr212.8mg were dissolved in 1mL of DMSO solution and stirred at 100 ℃ for 2 hours.
The invention has the beneficial effects that:
the dye-sensitized and double perovskite hybrid solar cell provided by the invention uses titanium dioxide sensitized by indole dyes D102, D131 or D149 as an electron transport layer and is based on Cs2AgBiBr6A solar cell as a perovskite layer. The indole dye sensitized titanium dioxide contributes to both the optical absorption and photocurrent of the device. Compared with devices prepared based on other electron transport materials, the device prepared by the preparation method provided by the invention has the advantages that the photocurrent is obviously improved, the highest photoelectric conversion efficiency reaches 4.23%, and the device is a non-lead double perovskite solar cell with the highest efficiency.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 shows Cs based on D149 sensitized titanium dioxide as an electron transport layer according to the present invention2AgBiBr6Scanning electron microscope images of the cross section of the efficient non-lead double perovskite solar cell.
Fig. 2 is a diagram of the energy level structure and electron transport path of the photovoltaic device of the present invention.
FIG. 3 shows indole dye-sensitized and double perovskite-based Cs prepared according to the present invention2AgBiBr6J-V plots of hybrid solar cell devices and indole dye-based sensitized solar cells.
Detailed Description
The invention provides a dye-sensitized and double-perovskite hybrid solar cell which sequentially comprises a transparent conductive glass cathode, an electron transport layer, a perovskite layer, a hole transport layer and a metal anode from bottom to top; the electron transport layer is TiO sensitized by indole dyes D102, D131 or D1492(ii) a The perovskite layer is Cs2AgBiBr6。
The indole dye is D102, D131 or D149 which is commercially produced and can be directly purchased, and the structure of the indole dye is as follows:
preferably, the transparent conductive glass cathode is fluorine-containing indium tin oxide (FTO); the electron transport layer is c-TiO2/m-TiO2C-Chl (wherein C-TiO)2Is a dense layer of titanium dioxide, m-TiO2Is mesoporous layer titanium dioxide); the hole transport layer is Spiro-OMeTAD; the metal anode is Ag.
The invention has no special requirements on the thickness of each layer of the dye-sensitized and double perovskite hybrid solar cell, and the required thickness can be prepared according to actual requirements. Preferably, the electron transport layer has a thickness of 470nm, the perovskite layer has a thickness of 210nm, the hole transport layer has a thickness of 70nm, and the metal anode has a thickness of 60 nm.
The invention also provides a preparation method of the dye-sensitized and double perovskite hybridized solar cell, which comprises the following steps:
1) and (3) treating a transparent conductive glass cathode:
carrying out ultraviolet ozone pretreatment on the cleaned transparent conductive glass for 20 minutes;
2) preparing and processing an electron transport layer:
placing the transparent conductive glass pretreated by ultraviolet ozone in the step 1) in a spin coater, spin-coating isopropyl titanate solution, rotating at 4000rpm for 30s, and then placing in a muffle furnace for annealing at 500 ℃ for 30 min; after the substrate is cooled, spin-coating titanium dioxide nano particle colloidal solution on the substrate, rotating at 2000rpm for 30s, and annealing at 500 ℃ for 30 minutes; annealing and placing the silicon carbide substrate on TiCl4In the solution, annealing is carried out for 30 minutes at the temperature and time of 70 ℃ and the annealing temperature and time of 1h of 500 ℃; after annealing, soaking the obtained product in acetonitrile and tert-butyl alcohol (volume ratio is 1: 1) solution of indole dye, wherein the concentration of the solution is 0.3 mg/mL;
3) preparation of perovskite layer:
subjecting perovskite precursor Cs2AgBiBr6The solution is placed on a hot bench at 100 ℃ and stirred for 2 hours by magnetic force, and after the solution is cooled to room temperature, the perovskite precursor Cs is added2AgBiBr6The solution was passed through a 20 micron filterFiltering; putting the device in the step 2) into a glove box filled with nitrogen, and spin-coating a perovskite precursor Cs on the electron transport layer2AgBiBr6The spin coating speed of the solution is 2000rpm, the time is 60 seconds, the solution is placed on a hot bench for annealing treatment after the spin coating is finished, and the annealing temperature and the annealing time are 200 ℃ for annealing for 10 minutes;
4) preparation of hole transport layer:
Spiro-OMeTAD was dissolved in chloroform solution at a concentration of 80mg/mL, 10.5. mu.L of 4-tert-butylpyridine (TBP) and 46.5. mu.L of Li-TFSI solution (170mg/mL in acetonitrile) were added, and after sufficient magnetic stirring, the Spiro-OMeTAD solution was spin-coated on the perovskite layer at 4000rpm for 30 seconds;
5) preparing a metal anode:
using vacuum evaporation coating machine to make pressure less than 6 x 10-4Evaporating metal anode on the hole transport layer at Pa with the evaporation rate of
The perovskite layer precursor Cs2AgBiBr6The preparation process of the solution is as follows:
in a nitrogen glove box, 0.5mMol of BiBr3224.3mg and 0.5mMol of AgBr93.9mg and 1mMol of CsBr212.8mg were dissolved in 1mL of DMSO solution and stirred at 280 ℃ for 2 hours.
In order to further understand the present invention, the following technical solutions are clearly and completely described with reference to the following embodiments, but the embodiments of the present invention are only for explaining the present invention and do not limit the present invention, and all other embodiments obtained by those skilled in the art without creative efforts belong to the protection scope of the present invention.
The starting materials used in the following examples are all commercially available products.
Examples
Sequentially carrying out ultrasonic treatment on the etched FTO for 30 minutes by using a cleaning agent, deionized water, acetone, alcohol and isopropanol, then preparing an isopropyl titanate solution, and mixing the deionized water, the isopropyl titanate and hydrochloric acidMixing the materials in a volume ratio of 100:10:1 to obtain isopropyl titanate solution. Pretreating FTO (fluorine-doped tin oxide) by ultraviolet ozone for 30 minutes, placing the FTO on a spin coater, spin-coating isopropyl titanate solution for 30 seconds at the rotating speed of 4000rpm, and immediately placing the FTO in a muffle furnace for annealing treatment at the annealing temperature and the annealing time of 500 ℃ for 30 minutes; preparing titanium dioxide nano particle colloidal solution, mixing titanium dioxide colloidal particles and ethanol according to the mass ratio of 1:2 to obtain the titanium dioxide nano particle colloidal solution, spin-coating the titanium dioxide nano particle colloidal solution at the rotating speed of 2000rpm for 30s, immediately placing the titanium dioxide nano particle colloidal solution in a muffle furnace for annealing treatment, and annealing for 30 minutes at the annealing temperature and the annealing time of 500 ℃; then preparing an aqueous titanium tetrachloride solution, adding 67.5. mu.L of the aqueous titanium tetrachloride solution into 10mL of ultrapure water to obtain an aqueous titanium tetrachloride solution, placing the substrate into the aqueous titanium tetrachloride solution and placing the substrate into an oven at 70 ℃ for 1 hour, and finally immersing the substrate in a solution of indole dyes D102, D131 or D149 in acetonitrile and tert-butyl alcohol (volume ratio of 1: 1) for 10 minutes. Preparing Cs in a nitrogen glove box2AgBiBr6Precursor solution, 0.5mMol of BiBr3(224.3mg) and 0.5mMol of AgBr (93.9mg) and 1mMol of CsBr (212.8mg) were dissolved in 1mL of DMSO solution and stirred at 100 ℃ for 2 hours. And (3) conveying the substrate into a glove box, spin-coating the perovskite precursor solution on the electron transport layer at the rotating speed of 2000rpm for 60 seconds, and after the spin-coating is finished, putting the substrate on a hot bench for annealing at the annealing temperature and the annealing time of 200 ℃ for 10 minutes. A solution of Spiro-OMeTAD was then prepared in a nitrogen glove box, dissolved in 80mg/mL chloroform, added with 10.5. mu.L of 4-tert-butylpyridine (TBP) and 46.5. mu.L of Li-TFSI solution (170mg/mL in acetonitrile), and after sufficient magnetic stirring, the Spiro-OMeTAD solution was spin-coated on the perovskite layer at 4000rpm for 30 seconds to form a Spiro-OMeTAD film. Finally, the substrate is sent into an organic evaporation coating machine, and when the pressure in the cavity is lower than 6 x 10-4Pa time silver electrode and evaporation rate thereofThe silver film thickness was 60 nm. Thus, the indole dye D102, D131 or D149-sensitized dioxide is obtainedTitanium as an electron transport layer, Cs2AgBiBr6A high efficiency non-lead double perovskite solar cell as a light absorbing layer. A cross-sectional sem image of the device is shown in fig. 1. The thickness of the electron transport layer in this example was 470nm, the thickness of the perovskite layer was 210nm, the thickness of the hole transport layer was 70nm and the thickness of the metal anode was 60 nm.
The thickness of the electron transport layer, the thickness of the perovskite layer, the thickness of the hole transport layer and the thickness of the metal anode in the above embodiments can also be prepared according to actual needs, and are not listed here.
Comparative example 1-1
The difference from example 1 is that comparative example 1-1 uses titanium dioxide which is not sensitized with indole dye as an electron transport material, and the rest of the preparation method is the same as example 1.
TABLE 1 Cs-based materials prepared with indole dye sensitized titanium dioxide and common titanium dioxide as electron transport layers, respectively2AgBiBr6The photovoltaic parameters of the high-efficiency perovskite solar cell device are different. Compared with a solar cell prepared based on common titanium dioxide, the solar cell prepared by taking the titanium dioxide sensitized by the indole dye as the electron transport layer has the advantage that the short-circuit current density is obviously improved. The photoelectric conversion efficiency of the D149-based device is as high as 4.23%.
TABLE 1
Fig. 2 is a diagram of the energy level structure and electron transport path of the photovoltaic device of the present invention. Electrons excited in the indole dye can be rapidly extracted by titanium dioxide, and the rest holes can directly obtain electrons from the LUMO energy level of the perovskite and can also be diffused to the hole transport layer through the Fermi energy level of the perovskite; excited holes in the perovskite can then be directly transferred into the hole transport layer. In this system, both indole dye and double perovskite are used as light absorbing materials to contribute to the photocurrent density of the cell.
FIG. 3 shows indole dye sensitized and double perovskite Cs prepared by the present invention2AgBiBr6J-V plots of hybrid high efficiency solar cell devices and corresponding data in table 1. The prepared Cs based on indole dye sensitization and double perovskites2AgBiBr6Compared with a device prepared by taking common titanium dioxide as an electron transport layer, the short-circuit current density of the hybrid high-efficiency solar cell is obviously improved, and the highest energy conversion efficiency reaches 4.23%.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (9)
1. A dye-sensitized and double-perovskite hybrid solar cell is characterized by sequentially comprising a transparent conductive glass cathode, an electron transport layer, a perovskite layer, a hole transport layer and a metal anode from bottom to top;
it is characterized in that the preparation method is characterized in that,
the electron transport layer is titanium dioxide sensitized by indole dyes D102, D131 or D149;
the structural formula of the indole dye D102, D131 or D149 is as follows:
the perovskite layer is Cs2AgBiBr6。
2. The hybrid dye-sensitized and double perovskite solar cell according to claim 1, characterized in that said transparent conductive glass cathode is fluorine doped indium tin oxide.
3. Root of herbaceous plantThe hybrid dye-sensitized and double perovskite solar cell according to claim 1, characterized in that said electron transport layer structure is c-TiO2/m-TiO2D102, D131 or D149.
4. The hybrid dye-sensitized and double perovskite solar cell according to claim 1, characterized in that the hole transport layer is 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene.
5. Hybrid solar cell according to claim 1, characterized in that the metal anode is Ag.
6. The hybrid dye-sensitized and double perovskite solar cell according to claim 1, characterized in that the thickness of the electron transport layer is 470nm, the thickness of the perovskite layer is 210nm, the thickness of the hole transport layer is 70nm and the thickness of the metal anode is 60 nm.
7. A method for preparing a hybrid solar cell of dye-sensitized and double perovskite according to claim 1, characterized in that it comprises the following steps:
1) and (3) treating a transparent conductive glass cathode:
carrying out ultraviolet ozone pretreatment on the cleaned transparent conductive glass;
2) preparing and processing an electron transport layer:
placing the transparent conductive glass pretreated by ultraviolet ozone in the step 1) in a spin coater, spin-coating an isopropyl titanate solution, then placing in a muffle furnace for annealing, placing in the spin coater again after annealing, spin-coating a titanium dioxide nano particle colloidal solution, randomly placing in the muffle furnace for annealing, and placing in TiCl after annealing4Finally, dipping the obtained product in acetonitrile and tert-butyl alcohol solution of indole dye to prepare an electron transport layer;
the indole dye is D102, D131 or D149;
3) preparation of perovskite layer:
subjecting perovskite precursor Cs2AgBiBr6The solution is placed on a hot bench for magnetic stirring, and after the solution is cooled to room temperature, the perovskite precursor Cs is added2AgBiBr6Filtering the solution through a filter membrane; then putting the device in the step 2) into a glove box filled with nitrogen, and spin-coating the perovskite precursor Cs on the electron transport layer2Placing the AgBiBr solution on a hot table for annealing treatment after the spin coating is finished, and preparing a perovskite layer;
4) preparation of hole transport layer:
spin coating on the perovskite layer to prepare a hole transport layer;
5) preparing a metal anode:
and evaporating a metal anode on the hole transport layer by using a vacuum evaporation coating machine.
8. The method for preparing a hybrid dye-sensitized and double perovskite solar cell according to claim 7, wherein one specific embodiment is as follows:
1) and (3) treating a transparent conductive glass cathode:
carrying out ultraviolet ozone pretreatment on the cleaned transparent conductive glass for 20 minutes;
2) preparing and processing an electron transport layer:
placing the transparent conductive glass pretreated by ultraviolet ozone in the step 1) in a spin coater, spin-coating isopropyl titanate solution, rotating at 4000rpm for 30s, and then placing in a muffle furnace for annealing at 500 ℃ for 30 min; after the substrate is cooled, spin-coating titanium dioxide nano particle colloidal solution on the substrate, rotating at 2000rpm for 30s, and annealing at 500 ℃ for 30 minutes; annealing and placing the silicon carbide substrate on TiCl4In the solution, the temperature and the time are kept at 70 ℃ for 1h, and the annealing temperature and the annealing time are kept at 500 ℃ for 30 minutes; and after the annealing is finished, soaking the obtained product in acetonitrile and tert-butyl alcohol solution of indole dye, wherein the solution concentration is 0.3mg/mL, and the volume ratio of the acetonitrile to the tert-butyl alcohol is 1: 1;
3) preparation of perovskite layer:
subjecting perovskite precursor Cs2AgBiBr6The solution is placed on a hot bench at 100 ℃ and stirred for 2 hours by magnetic force, and after the solution is cooled to room temperature, the perovskite precursor Cs is added2AgBiBr6Filtering the solution through a 20-micron filter membrane; putting the device in the step 2) into a glove box filled with nitrogen, and spin-coating a perovskite precursor Cs on the electron transport layer2AgBiBr6The spin coating speed of the solution is 2000rpm, the time is 60 seconds, the solution is placed on a hot bench for annealing treatment after the spin coating is finished, and the annealing temperature and the annealing time are 200 ℃ for annealing for 10 minutes;
4) preparation of hole transport layer:
dissolving Spiro-OMeTAD in chloroform solution at a concentration of 80mg/mL, adding 10.5. mu.L of 4-tert-butylpyridine and 46.5. mu.L of Li-TFSI solution dissolved in acetonitrile solution at a concentration of 170mg/mL, and after sufficient magnetic stirring, spin-coating Spiro-OMeTAD solution on the perovskite layer at a rotation speed of 4000rpm for 30 seconds;
5) preparing a metal anode:
9. The method for preparing hybrid dye-sensitized and double perovskite solar cell according to claim 8, characterized in that the perovskite layer precursor Cs2AgBiBr6The preparation process of the solution is as follows:
in a nitrogen glove box, 0.5mMol of BiBr3224.3mg and 0.5mMol of AgBr93.9mg and 1mMol of CsBr212.8mg were dissolved in 1mL of DMSO solution and stirred at 100 ℃ for 2 hours.
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