CN118382304A - Wide band gap perovskite solar cell, laminated cell and electricity utilization device - Google Patents
Wide band gap perovskite solar cell, laminated cell and electricity utilization device Download PDFInfo
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Abstract
The application relates to a wide-bandgap perovskite solar cell, a laminated cell and an electric device. The wide-bandgap perovskite solar cell comprises a first electrode layer, a functional layer and a second electrode layer which are sequentially laminated, wherein the functional layer comprises a perovskite film, and the preparation method of the perovskite film comprises the following steps: applying a precursor solution of the organic-inorganic hybrid perovskite material to the prefabricated member, and then adding an antisolvent to prepare an intermediate member; under the environment condition of isolating water and oxygen, carrying out primary annealing on the intermediate piece at 60-80 ℃ to prepare a first piece; and (3) carrying out secondary annealing on the first workpiece at 90-110 ℃ under the environment condition that the humidity is less than or equal to 30% RH and air. The wide-bandgap perovskite solar cell has better device performance, higher efficiency and low process cost.
Description
Technical Field
The application relates to the technical field of perovskite solar cells, in particular to a wide-bandgap perovskite solar cell, a laminated cell and an electricity utilization device.
Background
Single junction perovskite solar cells have been approaching their theoretical schotter-queter (S-Q) efficiency limit since 2009, and in recent years, the highest photoelectric conversion efficiencies approaching 26% have been rapidly achieved. In order to further improve the photoelectric conversion efficiency of the solar cell, the most potential method is to integrate a perovskite cell with a wide band gap (band gap is 1.68 eV) with a crystalline silicon cell to construct a serial laminated solar cell, and the perovskite cell with the band gap of 1.68eV is critical to realizing ideal current matching between the perovskite cell and the crystalline silicon cell in the perovskite/crystalline silicon laminated solar cell.
However, the current wide bandgap perovskite solar cell with 1.68eV still faces larger energy loss, and the process time is longer, the production cost is higher, and the device performance and the productivity are still to be further improved.
Disclosure of Invention
Based on the above, the application provides a wide-bandgap perovskite solar cell with better device performance, higher efficiency and low process cost, and a laminated cell and an electricity utilization device comprising the wide-bandgap perovskite solar cell.
According to a first aspect of the application, there is provided a wide bandgap perovskite solar cell comprising a first electrode layer, a functional layer and a second electrode layer laminated in sequence, the functional layer comprising a perovskite thin film, the preparation method of the perovskite thin film comprising the steps of:
Applying a precursor solution of the organic-inorganic hybrid perovskite material to the prefabricated member, and then adding an antisolvent to prepare an intermediate member;
Under the environment condition of isolating water and oxygen, carrying out primary annealing on the intermediate piece at 60-80 ℃ to prepare a first piece;
and (3) carrying out secondary annealing on the first workpiece at 90-110 ℃ under the environment condition that the humidity is less than or equal to 30% RH and air.
In one embodiment, the temperature of the first annealing is 65 ℃ to 75 ℃; and/or
The temperature of the second annealing is 95-105 ℃.
In one embodiment, the first annealing time is 1 to 5 minutes; and/or
And the time of the second annealing is 8-15 min.
In one embodiment, the structural general formula of the organic-inorganic hybrid perovskite material is Cs 0.22FA0.78Pb(I1-xBrx)3, wherein x is 0.15-0.2.
In one embodiment, the step of applying a precursor solution of an organic-inorganic hybrid perovskite material to the preform, and then adding an antisolvent comprises:
The spin coating treatment is performed after the precursor solution is applied to the preform, and the antisolvent is added before the spin coating treatment is completed.
In one embodiment, the spin-coating process conditions include: the rotating speed is 3000 rpm/min-5000 rpm/min, and the time is 40 s-60 s; and/or
And adding the antisolvent 20-35 s before the spin coating treatment is finished.
In one embodiment, the solvent of the precursor solution comprises one or both of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF), and the antisolvent comprises one or both of chlorobenzene and anisole.
In one embodiment, the volume ratio of the antisolvent to the precursor solution is 5:2-4:1.
In a second aspect of the application, a laminated cell is provided, comprising a perovskite cell and a crystalline silicon cell arranged in series, wherein the perovskite cell is the wide bandgap perovskite solar cell in the first aspect.
In a third aspect of the application, there is provided an electrical device comprising a wide bandgap perovskite solar cell as described in the first aspect or a stacked cell as described in the second aspect.
The wide band gap perovskite solar cell is based on a high-performance organic-inorganic hybrid perovskite material system, is matched with an antisolvent method, and performs intermediate phase precipitation under the anhydrous and anaerobic conditions, so that the quality of the intermediate phase can be effectively improved, and then the intermediate phase is further annealed under certain humidity and temperature conditions, so that the quality of a wide band gap perovskite film can be effectively improved, the defect density is reduced, and the device performance is improved. Meanwhile, the perovskite film has short preparation process time, high production efficiency and low cost, and is beneficial to large-scale production.
Detailed Description
The wide band gap perovskite solar cell, the stacked cell and the electric device according to the present application will be described in further detail with reference to specific examples. The present application may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
The term "and/or," "and/or," as used herein, includes any one of two or more of the listed items in relation to each other, as well as any and all combinations of the listed items in relation to each other, including any two of the listed items in relation to each other, any more of the listed items in relation to each other, or all combinations of the listed items in relation to each other.
Herein, "one or more" refers to any one, any two, or any two or more of the listed items.
In the present application, "first aspect", "second aspect", "third aspect", "fourth aspect", etc. are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity, nor as implying an importance or quantity of technical features indicated. Moreover, the terms "first," "second," "third," "fourth," and the like are used for non-exhaustive list description purposes only, and are not to be construed as limiting the number of closed forms.
In the application, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
In the present application, the numerical ranges are referred to as continuous, and include the minimum and maximum values of the ranges, and each value between the minimum and maximum values, unless otherwise specified. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
The percentage content referred to in the present application refers to mass percentage for both solid-liquid mixing and solid-solid mixing and volume percentage for liquid-liquid mixing unless otherwise specified.
The percentage concentrations referred to in the present application refer to the final concentrations unless otherwise specified. The final concentration refers to the ratio of the additive component in the system after the component is added.
The temperature parameter in the present application is not particularly limited, and may be a constant temperature treatment or a treatment within a predetermined temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
The room temperature in the present application is generally 4 ℃ to 30 ℃, preferably 20+ -5 ℃.
Currently, a wide bandgap perovskite solar cell with 1.68eV suffers from a larger energy loss, which is mainly related to the defect of having more deep energy levels in a low quality wide bandgap perovskite film, resulting in more serious non-radiative recombination loss, so that there is a need for an effective method to reduce the energy loss of the wide bandgap perovskite film. In addition, in order to obtain a high-quality wide-bandgap perovskite film, a longer crystallization time (generally about 30 min) is generally required in the conventional method, so that the process time of the wide-bandgap perovskite solar cell is longer, the production cost is higher, the productivity is lower, and the large-scale production is not facilitated.
Based on this, some examples of the present application provide a wide bandgap perovskite solar cell including a first electrode layer, a functional layer, and a second electrode layer laminated in this order, the functional layer including a perovskite thin film, the perovskite thin film manufacturing method including the steps of:
Applying a precursor solution of the organic-inorganic hybrid perovskite material to the prefabricated member, and then adding an antisolvent to prepare an intermediate member;
Under the environment condition of isolating water and oxygen, carrying out primary annealing on the intermediate piece at 60-80 ℃ to prepare a first piece;
and (3) carrying out secondary annealing on the first workpiece at 90-110 ℃ under the environment condition that the humidity is less than or equal to 30% RH and air.
The wide band gap perovskite solar cell is based on a high-performance organic-inorganic hybrid perovskite material system, is matched with an antisolvent method, performs intermediate phase annealing precipitation under the anhydrous and anaerobic conditions, removes the solvent in the intermediate phase, simultaneously can effectively improve the quality of the intermediate phase, and further anneals under certain humidity and temperature conditions, wherein the humidity in the atmosphere can promote the vaporization of hygroscopic components in the thermal annealing process, is beneficial to stabilizing the photoactive alpha-phase perovskite structure, and the oxygen in the air anneals in the low humidity environment to passivate the defects of the perovskite film, so that the quality of the wide band gap perovskite film is effectively improved, the defect density is reduced, and the device performance is improved. Meanwhile, the perovskite film has short preparation process time, high production efficiency and low cost, and is beneficial to large-scale production.
It will be understood that the "preform" refers to an intermediate article of a perovskite solar cell which has been prepared prior to the preparation of the perovskite thin film, for example, comprising a first electrode layer (for example, ITO glass) and a hole transporting layer (for example, [2- (3, 6-dimethoxy-9-hydro-carbazol-9-yl) ethyl ] phosphoric acid, meO-2 PACZ) laminated in this order, and after the preparation of the perovskite thin film on the surface of the hole transporting layer is completed according to the procedure described above, the preparation of an electron transporting layer (for example, C 60), a hole blocking layer (for example, BCP) and a second electrode layer (for example, ag) may be continued on the surface of the perovskite thin film.
Specifically, during the first anneal, the temperature includes, but is not limited to: 60 ℃, 62 ℃, 64 ℃, 65 ℃, 66 ℃, 68 ℃, 70 ℃, 72 ℃, 74 ℃, 75 ℃, 76 ℃, 78 ℃, 80 ℃, or a range between any two of the foregoing. Further, the temperature of the first annealing is 65-75 ℃.
In some examples, the first anneal is 1 to 5 minutes. Specifically, the time of the first annealing includes, but is not limited to: 1min, 2min, 3min, 4min, 5min, or a range therebetween.
Specifically, during the second anneal, the temperatures include, but are not limited to: 90 ℃, 92 ℃, 94 ℃, 95 ℃, 96 ℃, 98 ℃, 100 ℃, 102 ℃, 104 ℃, 105 ℃, 106 ℃, 108 ℃, 110 ℃, or a range between any two of the foregoing. Further, the temperature of the second annealing is 95-105 ℃.
In some examples, the second annealing time is 8min to 15min. Specifically, the time of the second annealing includes, but is not limited to: 8min, 9min, 10min, 11min, 12min, 13min, 14min, 15min, or a range therebetween.
In some examples, humidity during the second anneal includes, but is not limited to: 5% RH, 10% RH, 15% RH, 18% RH, 20% RH, 22% RH, 25% RH, 30% RH, or a range between any two of the foregoing.
In addition, in some examples, the structural general formula of the organic-inorganic hybrid perovskite material is Cs 0.22FA0.78Pb(I1-xBrx)3, where x is 0.15-0.2.
In some of these examples, the step of applying a precursor solution of the organic-inorganic hybrid perovskite material to the preform, and then adding the antisolvent comprises:
The spin coating treatment is performed after the precursor solution is applied to the preform, and the antisolvent is added before the spin coating treatment is completed.
In some examples, the conditions of the spin-coating process include: the rotating speed is 3000 rpm/min-5000 rpm/min, and the time is 40 s-60 s. Specifically, rotational speeds include, but are not limited to: 3000rpm/min, 3500rpm/min, 4000rpm/min, 4500rpm/min, 5000rpm/min or a range between any two of the foregoing. Time includes, but is not limited to: 40s, 45s, 50s, 55s, 60s or a range between any two of the foregoing.
In some examples, the antisolvent is added 20 s-35 s before the spin-coating process is completed. Specifically, the time for adding the antisolvent is 20s, 25s, 28s, 30s, 32s or 35s before the spin-coating treatment is finished.
In some examples, the solvent of the precursor solution includes one or both of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF). Further, the solvent of the precursor solution comprises a combination of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF), and the volume ratio of the two can be 1:3-1:4.
In some examples, the antisolvent comprises one or both of chlorobenzene and anisole. When a combination of chlorobenzene and anisole is employed, the ratio of the two may be optional.
In some examples, the volume ratio of the antisolvent to the precursor solution is 5:2-4:1. Specifically, the volume ratio of the antisolvent to the precursor solution includes, but is not limited to: 5:2, 3:1, 3.5:1, 4:1, or a range between any two of the foregoing.
Still other examples of the present application provide a stacked cell comprising a perovskite cell and a crystalline silicon cell arranged in series, the perovskite cell being a wide bandgap perovskite solar cell as described above.
Still other examples of the application provide an electrical device comprising a wide bandgap perovskite solar cell as described above or a stacked cell as described above.
The experimental parameters not specified in the following specific examples are preferentially referred to the guidelines given in the present document, and may also be referred to the experimental manuals in the art or other experimental methods known in the art, or to the experimental conditions recommended by the manufacturer.
The starting materials and reagents referred to in the following specific examples may be obtained commercially or may be prepared by known means by those skilled in the art.
Example 1
The embodiment is a wide-bandgap perovskite solar cell, which is prepared by the following steps:
1) Cleaning and preparing ITO glass: cleaning a transparent conductive substrate (ITO glass), and sequentially cleaning the transparent conductive substrate with deionized water, acetone and isopropanol for 15 minutes; after cleaning, drying the substrate by a nitrogen gun, placing the substrate in an ultraviolet ozone cleaner for cleaning for 20 minutes, and placing the substrate in a container for transferring into a glove box for standby after cleaning;
2) Preparation of hole transport layer: in a glove box, taking a certain amount of prepared hole transport layer solution (MeO-2 PACz, the concentration is 1.5mg/mL, and the solvent is methanol), dripping the solution on a substrate, performing spin coating preparation, placing the substrate on a hot table after spin coating is finished, annealing and crystallizing at a constant temperature, and cooling to room temperature for standby after crystallization is finished;
3) Preparation of perovskite thin film:
Preparing a precursor solution according to an inorganic hybridization perovskite material Cs 0.22FA0.78Pb(I1-xBrx)3 (x is 0.2), wherein the solvent is a mixed solvent of DMSO and DMF (volume ratio is 1:3); dripping the precursor solution on the surface of the hole transport layer, spin-coating for 50s at 4000rpm/min, rapidly dripping 150 mu L of antisolvent (the type is chlorobenzene and the volume ratio of the spin-coated precursor solution is 3:1) at the height of 1cm before the spin-coating process is finished for about 30s, and then continuously completing the spin-coating to prepare a middleware; firstly, placing the intermediate piece in a glove box without water and oxygen, adopting 70 ℃ for annealing for 2min, then transferring the intermediate piece out of the glove box by a vertical horse, continuously annealing for 10min at 100 ℃ in an atmosphere with humidity of 25% RH, preparing a wide band gap perovskite film, and cooling to room temperature for later use;
4) Preparation of an electron transport layer: based on the prepared perovskite film, transferring the perovskite film into a thermal evaporation chamber, vacuumizing, and depositing a C 60 film with the thickness of 25nm at the rate of 0.2A/s after the vacuum degree reaches below 10 -4 Pa to finish the preparation of an electron transport layer;
5) Preparation of hole blocking layer: after the C 60 is evaporated, continuously depositing a BCP film with the thickness of 8nm at the speed of 0.2A/s in a chamber with the vacuum degree of 10 -4 Pa or less;
6) Preparation of a second electrode layer: after the BCP is deposited, a metal Ag film with the thickness of 100nm is deposited in a chamber with the vacuum degree of less than 10 -4 Pa at the speed of 1.4A/s.
Example 2
The present embodiment is a wide bandgap perovskite solar cell, and the preparation steps are the same as those of embodiment 1, and the main difference is that: the temperature of the first annealing was 60℃and the time was 5min.
Example 3
The present embodiment is a wide bandgap perovskite solar cell, and the preparation steps are the same as those of embodiment 1, and the main difference is that: the temperature of the second annealing was 110℃for 8min.
Example 4
The present embodiment is a wide bandgap perovskite solar cell, and the preparation steps are the same as those of embodiment 1, and the main difference is that: during the second anneal, the humidity was 10% RH.
Comparative example 1
This comparative example is a wide bandgap perovskite solar cell, which is prepared by the same procedure as example 1, with the main differences: the temperature of the first annealing was 40℃and the time was 4min.
Comparative example 2
This comparative example is a wide bandgap perovskite solar cell, which is prepared by the same procedure as example 1, with the main differences: the temperature of the second annealing was 120℃for 10min.
Comparative example 3
This comparative example is a wide bandgap perovskite solar cell, which is prepared by the same procedure as example 1, with the main differences: both anneals were performed in an anhydrous, oxygen-free glove box. The method comprises the following specific steps: the intermediate piece is placed in a glove box without water and oxygen, and is annealed at 100 ℃ for 30min to prepare the perovskite film with wide band gap.
Test example:
The testing method comprises the following steps: the test in a glove box, the temperature of the glove box is about 25 ℃, the water and oxygen content is less than 0.01ppm, the J-V curve of a battery device passes through the Keithley 2400 source list test, the light source AM1.5G,100mW/cm 2, the light source intensity passes through the standard silicon battery calibration, the voltage test range is-0.1V-1.3V, the step length is 0.01V, and the delay time is 50ms.
The test results are shown in table 1 below:
TABLE 1
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples merely illustrate a few embodiments of the present application, which are convenient for a specific and detailed understanding of the technical solutions of the present application, but should not be construed as limiting the scope of the claims. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. It should be understood that, based on the technical solutions provided by the present application, those skilled in the art may obtain technical solutions through logical analysis, reasoning or limited experiments, which are all within the scope of protection of the appended claims. The scope of the patent of the application should therefore be determined with reference to the appended claims, which are to be construed as in accordance with the doctrines of claim interpretation.
Claims (10)
1. The wide-bandgap perovskite solar cell is characterized by comprising a first electrode layer, a functional layer and a second electrode layer which are sequentially stacked, wherein the functional layer comprises a perovskite film, and the preparation method of the perovskite film comprises the following steps:
Applying a precursor solution of the organic-inorganic hybrid perovskite material to the prefabricated member, and then adding an antisolvent to prepare an intermediate member;
Under the environment condition of isolating water and oxygen, carrying out primary annealing on the intermediate piece at 60-80 ℃ to prepare a first piece;
and (3) carrying out secondary annealing on the first workpiece at 90-110 ℃ under the environment condition that the humidity is less than or equal to 30% RH and air.
2. The wide bandgap perovskite solar cell of claim 1, wherein the temperature of said first annealing is 65 ℃ to 75 ℃; and/or
The temperature of the second annealing is 95-105 ℃.
3. The wide bandgap perovskite solar cell of claim 1, wherein the time of the first annealing is 1 to 5 minutes; and/or
And the time of the second annealing is 8-15 min.
4. The wide band gap perovskite solar cell according to claim 1, wherein the organic-inorganic hybrid perovskite material has a general structural formula of Cs 0.22FA0.78Pb(I1-xBrx)3, wherein x is 0.15-0.2.
5. The wide band gap perovskite solar cell according to any one of claims 1 to 4, wherein the step of applying a precursor solution of an organic-inorganic hybrid perovskite material to the preform, followed by adding an antisolvent comprises:
The spin coating treatment is performed after the precursor solution is applied to the preform, and the antisolvent is added before the spin coating treatment is completed.
6. The wide band gap perovskite solar cell of claim 5, wherein the spin-coating process conditions comprise: the rotating speed is 3000 rpm/min-5000 rpm/min, and the time is 40 s-60 s; and/or
And adding the antisolvent 20-35 s before the spin coating treatment is finished.
7. The wide band gap perovskite solar cell of any one of claims 1-4, wherein the solvent of the precursor solution comprises one or both of dimethyl sulfoxide and N, N-dimethylformamide, and the antisolvent comprises one or both of chlorobenzene and anisole.
8. The wide bandgap perovskite solar cell of claim 7, wherein the volume ratio of said antisolvent to said precursor solution is 5:2-4:1.
9. A laminated cell comprising a perovskite cell and a crystalline silicon cell arranged in series, wherein the perovskite cell is the wide band gap perovskite solar cell according to any one of claims 1 to 8.
10. An electrical device comprising the wide band gap perovskite solar cell according to any one of claims 1 to 8 or the stacked cell according to claim 9.
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| YUE YU, ET AL.: "Synergistic Effects of Lead Thiocyanate Additive and Solvent Annealing on the Performance of Wide-Bandgap Perovskite Solar Cells", ACS ENERGY LETT., vol. 2, 26 April 2017 (2017-04-26), pages 1177 * |
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