CN115666198A - Mixed solvent system, perovskite active layer and preparation method thereof, perovskite solar cell and preparation method thereof - Google Patents
Mixed solvent system, perovskite active layer and preparation method thereof, perovskite solar cell and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a mixed solvent system, a perovskite active layer and a preparation method thereof, and a perovskite solar cell and a preparation method thereof, wherein the mixed solvent system is used for being added into a perovskite precursor solution, and comprises the following raw materials: chloroisooctane, N-ethyl-2-pyrrolidone and dimethyl sulfoxide. The chloro-isooctane inhibits the reactivity of iodide and formamide ions through various chemical bonds, and ensures the stability of the precursor solution. In addition, due to Pb 2+ Chelation with Cl = O oxygen in chloroisooctane, chloroisooctane in perovskite membranes improves membrane quality at desired stoichiometry by reducing defect and lead iodide content. Precursor solution and phase doped with chloroisooctaneThe device has good performance reproducibility and super stability for more than 50 days under the environmental condition.
Description
Technical Field
The invention relates to the technical field of perovskite solar cells, in particular to a mixed solvent system, a perovskite active layer and a preparation method thereof, and a perovskite solar cell and a preparation method thereof.
Background
The perovskite is a material structure with very high photoelectric conversion efficiency, and has wide application and high attention. Perovskite (molecular general formula is ABX) 3 Of the class of crystalline materials) that was first discovered by the german scientist GustavRose in 1839 to have an elemental composition of CaTiO 3 Minerals, later referred to as perovskites, have such a crystalline structure. In perovskite octahedral junctionIn the structure, A is a larger cation, B is a smaller cation, X is an anion, and each A ion is surrounded by octahedra formed by B and X ions together. Perovskite materials are considered to be one of the most promising photoelectric materials of the next generation due to the advantages of high light absorption coefficient, high carrier mobility, simple synthesis method and the like.
Solution processing of perovskite solar cells is a promising option for high throughput production of low cost devices. Despite the great advances made in power conversion efficiency of perovskite solar cells, challenges remain in terms of reproducibility of the stability of the precursor solution, which is also improved.
Disclosure of Invention
The invention mainly aims to provide a mixed solvent system, a perovskite active layer and a preparation method thereof, a perovskite solar cell and a preparation method thereof, and aims to improve the stability of a precursor solution of the perovskite solar cell and the performance of a corresponding device.
In order to achieve the above object, the present invention provides a mixed solvent system, which is used to be added into a perovskite precursor solution, and comprises the following raw materials: chloroisooctane, N-ethyl-2-pyrrolidone and dimethyl sulfoxide.
Alternatively, the volume ratio of the dimethyl sulfoxide to the N-ethyl-2-pyrrolidone is 0.3:1 to 5:1.
alternatively, the volume ratio of the dimethyl sulfoxide to the N-ethyl-2-pyrrolidone is 0.3:1 to 2:1.
optionally, a ratio of the total moles of the chloroisooctane, the N-ethyl-2-pyrrolidone, and the moles of Pb ions in the perovskite precursor solution is 0.5:1 to 0.8:1.
the invention also provides a perovskite active layer which is formed by adding the mixed solvent system into the precursor solution and coating the precursor solution on an electron transport layer.
Optionally, the thickness of the perovskite active layer is 100 to 1000nm.
The invention further provides a preparation method of the perovskite active layer, which comprises the following steps:
providing the mixed solvent system, and dissolving methyl ammonium iodide and lead iodide in the mixed solvent system to prepare a precursor solution;
and dropwise adding the precursor onto the surface of the electron transport layer, and spin-coating to prepare a film to obtain the perovskite active layer.
The invention also provides a perovskite solar cell comprising the perovskite active layer as described above.
Optionally, the perovskite solar cell includes a conductive glass substrate, an electron transport layer, a hole transport layer and a metal electrode, which are sequentially stacked, and the perovskite active layer is disposed between the electron transport layer and the hole transport layer.
The invention also provides a preparation method of the perovskite solar cell, which comprises the following steps:
cleaning a substrate;
preparing a hole transport layer;
preparing a precursor solution of the perovskite active layer;
preparing a perovskite active layer;
preparing an electron transport layer;
and (5) evaporating a metal electrode.
In the technical scheme provided by the invention, chloroisooctane, N-ethyl-2-pyrrolidone and dimethyl sulfoxide are introduced into the perovskite precursor solution, wherein the chloroisooctane inhibits the reactivity of iodide and formamide ions through various chemical bonds, so that the stability of the precursor solution is ensured. In addition, due to Pb 2+ Chelation with Cl = O oxygen in chloroisooctane, which improves membrane quality at the desired stoichiometry by reducing defect and lead iodide content. The precursor solution doped with chloro-isooctane and the corresponding device have good performance reproducibility and super stability for more than 50 days under the environmental condition, and have the commercial feasibility of expandable manufacturing.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other related drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic diagram of the basic structure of a perovskite solar cell of the present invention;
fig. 2 is a graph of electrical properties of perovskite solar cells prepared according to examples of the present invention and comparative examples.
The reference numbers indicate:
| reference numerals | Name (R) | Reference numerals | Name(s) |
| 0 | Substrate and method of manufacturing the same | 3 | Perovskite active layer |
| 1 | Conductive glass substrate | 4 | |
| 2 | |
5 | Metal electrode |
The implementation, functional features and advantages of the present invention will be further described with reference to the accompanying drawings.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B" including either A or B or both A and B. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Solution processing of perovskite solar cells is a promising option for high throughput production of low cost devices. Despite the great advances made in power conversion efficiency of perovskite solar cells, challenges remain in terms of reproducibility of the stability of the precursor solution, which is also improved.
In view of this, the invention provides a mixed solvent system, which aims to solve the problem of stability of a precursor solution of a perovskite solar cell. In the attached drawings, fig. 1 is a basic structure schematic diagram of a perovskite solar cell of the invention; fig. 2 is a graph of electrical properties of perovskite solar cells prepared in examples of the present invention and comparative examples.
The invention provides a mixed solvent system which is used for being added into a perovskite precursor solution, and the mixed solvent system comprises the following raw materials: chloroisooctane, N-ethyl-2-pyrrolidone and dimethyl sulfoxide.
The mixed solvent system provided by the invention is suitable for various perovskite systems such as MAPbI 3 ，FAPbI 3 、CsFAPbI 3 、CsFAPbI 3 -XBr x And the like. The invention introduces chloroisooctane, N-ethyl-2-pyrrolidone and dimethyl sulfoxide into the perovskite precursor solution, wherein the chloroisooctane inhibits the reactivity of iodide and formamide ions through various chemical bonds, thereby ensuring the stability of the precursor solution. In addition, due to Pb 2+ Chelation with Cl = O oxygen in chloroisooctane, chloroisooctane in perovskite membranes improves membrane quality at desired stoichiometry by reducing defect and lead iodide content. The precursor solution doped with chloro-isooctane and the corresponding device have good performance reproducibility and super stability for more than 50 days under the environmental condition, and have the commercial feasibility of expandable manufacturing.
Wherein, the structural formula of the chloroisooctane is shown as the following formula:
the structural formula of the N-ethyl-2-pyrrolidone is shown as follows:
in this embodiment, the volume ratio of the dimethylsulfoxide to the N-ethyl-2-pyrrolidone is 0.3.
Further, in this example, the volume ratio of the dimethylsulfoxide to the N-ethyl-2-pyrrolidone is 0.3 to 1.
In this embodiment, the ratio of the total moles of the chloroisooctane and the N-ethyl-2-pyrrolidone to the moles of Pb ions in the perovskite precursor solution is 0.5 to 0.7, preferably, the ratio of the total moles of the chloroisooctane and the N-ethyl-2-pyrrolidone to the moles of Pb ions in the perovskite precursor solution is 0.5 to 1.0.8.
The invention also provides a perovskite active layer which is formed by adding the mixed solvent system into the precursor solution and coating the precursor solution on an electron transport layer, and the defects of the traditional perovskite battery can be reduced after the precursor solution added with the mixed solvent of the invention is coated on the electron transport layer.
Further, the material of the perovskite active layer comprises ABX 3 A compound of the formula (I), wherein A comprises K + 、Rb + 、Cs + 、CH 3 NH 3 + Or CH (NH) 2 ) 2+ And B comprises Pb 2+ X includes Cl - 、Br - 、I - Or SCN - The materials are simple in preparation process and low in cost, and meanwhile, the materials are more stable in structure and beneficial to diffusion and migration of defects.
Furthermore, the thickness of the perovskite active layer is 100-1000 nm, and in the range, the speed of electrons in the transmission process is high, so that the conversion efficiency can be improved.
The invention also provides a preparation method of the perovskite active layer, which comprises the following steps:
s1, providing the mixed solvent system, and dissolving methyl ammonium iodide and lead iodide in the mixed solvent system to prepare a precursor solution;
s2, dripping the precursor onto the surface of the electron transport layer, and spin-coating to prepare a film to obtain the perovskite active layer.
The preparation of the perovskite active layer comprises two parts of precursor liquid preparation and thin film deposition: preparing a precursor solution by mixing Methyl Ammonium Iodide (MAI) and lead iodide (PbI 2) in a ratio of 1:1 in a solvent system; the film deposition adopts any one of the conventional solution film forming methods such as a spin coating method, a wire bar coating method, a scraper coating method, a slit extrusion coating method, screen printing, gravure printing, letterpress printing and the like, preferably, the perovskite active layer is prepared by the spin coating method, and the high-efficiency perovskite light absorption layer is prepared by the one-step spin coating method. Preferably, the spin coating preparation of the active layer is divided into two stages, wherein the first stage is a slow stage, the preferred spin coating speed is 1000-3000 rpm/min, and the spin coating time is 1-5 seconds; the second stage is a high-speed stage, the preferred spin coating speed is 4000-6000 rpm/min, and the spin coating time is 30-50 seconds. The perovskite active layer prepared by the method is beneficial to reducing defects, so that the electron transmission rate is improved.
The invention also provides a perovskite solar cell which comprises the perovskite active layer, and the photoelectric conversion performance of the perovskite solar cell applying the perovskite active layer is improved.
Further, referring to fig. 1, the perovskite solar cell includes a conductive glass substrate 1, an electron transport layer 2, a hole transport layer 4 and a metal electrode 5, which are sequentially stacked, and the perovskite active layer 3 is disposed between the electron transport layer and the hole transport layer.
The material of the conductive glass substrate is usually a hard substrate such as commercial high-transmittance FTO glass and ITO glass, or a flexible substrate material (PET, PEN, PI, PC film, etc.) covered with ITO; the material of the electron transport layer is usually TiO 2 、SnO 2 、PCBM、C 60 And BCP, or a combination of two or more of them; preferably, the electron transport layer isSnO 2 And TiO 2 The combined film of (1). Wherein SnO 2 The film is prepared above the FTO film by adopting a hydrothermal deposition process, and the thickness of the film is 5-10 nm; tiO 2 2 The thin film is deposited above the FTO conductive thin film layer by adopting a high-temperature spraying process, and the thickness of the thin film is 5-10 nm; the material of the hole transport layer is usually 100-200 nm, and is usually formed by mixing Spiro-OMeTAD, CBZ, 1ul Li-TFSIFK209 and TBP. Preferably, the Spiro-OMeTAD film is prepared by a spin coating method with spin coating speed of 3000-5000 rpm/min. The metal electrode layer is one or a composite electrode of two or more selected from gold, copper, silver, aluminum and conductive carbon material electrodes.
The invention also provides a preparation method of the perovskite solar cell, which is characterized by comprising the following steps:
1. cleaning a substrate;
2. preparing a hole transport layer;
3. preparing a precursor solution of the perovskite active layer;
4. preparing a perovskite active layer;
5. preparing an electron transport layer;
6. and (5) evaporating a metal electrode.
The substrate cleaning refers to that a substrate material covering the transparent conductive electrode and flexible substrates such as FTO glass, PET, PC, PI and the like are ultrasonically cleaned twice by surfactant, deionized water, acetone and isopropanol in sequence, each time lasts for 10-15 minutes, then drying or blow-drying is carried out by nitrogen, and ultraviolet ozone (UVO) or plasma is subjected to surface treatment for 10-20 minutes for later use. The perovskite solar cell prepared by the scheme has better photoelectric conversion performance.
The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, it should be understood that the following examples are merely illustrative of the present invention and are not intended to limit the present invention.
Example 1
A mixed solvent system comprising the following raw materials: the perovskite precursor solution comprises chloroisooctane, N-ethyl-2-pyrrolidone and dimethyl sulfoxide, wherein the volume ratio of the dimethyl sulfoxide to the N-ethyl-2-pyrrolidone is 0.3.
Example 2
A mixed solvent system comprising the following raw materials: the perovskite precursor solution comprises chloroisooctane, N-ethyl-2-pyrrolidone and dimethyl sulfoxide, wherein the volume ratio of the dimethyl sulfoxide to the N-ethyl-2-pyrrolidone is 0.5.
Example 3
A mixed solvent system comprising the following raw materials: the perovskite precursor solution comprises chloroisooctane, N-ethyl-2-pyrrolidone and dimethyl sulfoxide, wherein the volume ratio of the dimethyl sulfoxide to the N-ethyl-2-pyrrolidone is 1.5, and the ratio of the total mole number of the chloroisooctane and the N-ethyl-2-pyrrolidone to the mole number of Pb ions in the perovskite precursor solution is 0.8.
Example 4
A mixed solvent system comprising the following raw materials: the perovskite precursor solution comprises chloroisooctane, N-ethyl-2-pyrrolidone and dimethyl sulfoxide, wherein the volume ratio of the dimethyl sulfoxide to the N-ethyl-2-pyrrolidone is 2.5, and the ratio of the total mole number of the chloroisooctane and the N-ethyl-2-pyrrolidone to the mole number of Pb ions in the perovskite precursor solution is 0.8.
Example 5
A mixed solvent system comprising the following raw materials: the perovskite precursor solution comprises chloroisooctane, N-ethyl-2-pyrrolidone and dimethyl sulfoxide, wherein the volume ratio of the dimethyl sulfoxide to the N-ethyl-2-pyrrolidone is 5.
Example 6
A mixed solvent system comprising the following raw materials: the perovskite precursor solution comprises chloroisooctane, N-ethyl-2-pyrrolidone and dimethyl sulfoxide, wherein the volume ratio of the dimethyl sulfoxide to the N-ethyl-2-pyrrolidone is 2.2.
Example 7
(1) Cleaning the FTO glass etched and processed by the femtosecond laser by the method, and carrying out UVO treatment for 15 minutes for later use;
(2) Preparing SnO with the thickness of 20nm by using the treated FTO glass through a CBD (chemical bath deposition) process 2 An electron transport layer;
(3) Coated SnO 2 Placing the FTO glass of the electron transmission layer into a titanium-based heating table, annealing for 60 minutes at 200 ℃, cooling, and taking out for later use;
(4) Taking 461.5mg of PbI 2 142.8mg of FAI (1H-imidazol-1-yl (2-methyl-3-furanyl) methanone) dissolved in 90. Mu.l of the mixed solvent system from example 1, DIO (1, 8-diiodooctane) added in an amount corresponding to that of PbI 2 The molar ratio of (1) to (2) is 0.65, and the total concentration of solute in the solution is 1.12mol/ml.
(5) SnO obtained in step (3) 2 Spin-coating the perovskite precursor solution obtained in the step (4) on an electron transport layer: the whole spin coating process is divided into three steps, firstly spin coating for 5 seconds at 5000 rpm/min; then spin-coating at 6000rpm/min for 30 seconds; the thickness of the obtained perovskite light absorption layer is controlled to be about 600 nm;
(6) Annealing the component obtained in the step (5) at 70 ℃ for 10 minutes in a nitrogen environment, cooling and taking out the component in an air environment with the humidity of 45%;
(7) Transferring the assembly prepared in the step (6) into a glove box in a nitrogen environment, mixing 54.75mg of Spiro-OMeTAD with 750ul of CBZ, 13.5ul of Li-TFSI, 21.75ul of FK209 and 22.5ul of TBP, and spin-coating at 4000rpm for 30s to obtain a hole transport layer;
(8) The assembly prepared in the step (7) is also used for preparing a gold electrode by adopting a thermal evaporation deposition method, and the vacuum degree is controlled to be lower than 4 x 10 -4 Pa, the evaporation rate is 1-2 angstroms/second, and the thickness of the gold electrode is 100nm, so that the perovskite solar cell device is prepared.
Example 8
(1) Cleaning the FTO glass etched and processed by the femtosecond laser by the method, and then carrying out UVO treatment for 15 minutes for later use;
(2) The treated FTO glass is prepared by a CBD (chemical water bath deposition) processSnO 20nm thick 2 An electron transport layer;
(3) Coated SnO 2 Placing the FTO glass of the electron transmission layer into a titanium-based heating table, annealing for 60 minutes at 200 ℃, cooling, and taking out for later use;
(4) Taking 461.5mg of PbI 2 142.8mg of FAI (1H-imidazol-1-yl (2-methyl-3-furanyl) methanone) dissolved in 90. Mu.l of the mixed solvent system of example 2, DIO (1, 8-diiodooctane) added in an amount corresponding to that of PbI 2 The molar ratio of (1) is 0.65, and the total concentration of solute in the solution is 1.12mol/ml.
(5) SnO obtained in step (3) 2 Spin-coating the perovskite precursor solution obtained in the step (4) on an electron transport layer: the whole spin coating process is divided into three steps, firstly spin coating for 5 seconds at 5000 rpm/min; then spin-coating at 6000rpm/min for 30 seconds; the thickness of the obtained perovskite light absorption layer is controlled to be about 600 nm;
(6) Annealing the component obtained in the step (5) at 70 ℃ for 10 minutes in a nitrogen environment, cooling and taking out the component in an air environment with the humidity of 45%;
(7) Transferring the assembly prepared in the step (6) into a glove box in a nitrogen environment, mixing 54.75mg of Spiro-OMeTAD with 750ul of CBZ, 13.5ul of Li-TFSI, 21.75ul of FK209 and 22.5ul of TBP, and spin-coating at 4000rpm for 30s to obtain a hole transport layer;
(8) The assembly prepared in the step (7) is also used for preparing a gold electrode by adopting a thermal evaporation deposition method, and the vacuum degree is controlled to be lower than 4 x 10 -4 Pa, the evaporation rate is 1-2 angstroms/second, and the thickness of the gold electrode is 100nm, so that the perovskite solar cell device is prepared.
Example 9
(1) Cleaning the FTO glass etched and processed by the femtosecond laser by the method, and then carrying out UVO treatment for 15 minutes for later use;
(2) Preparing SnO with the thickness of 20nm by using the treated FTO glass through a CBD (chemical bath deposition) process 2 An electron transport layer;
(3) Coated SnO 2 Placing the FTO glass of the electron transmission layer into a titanium-based heating table, annealing for 60 minutes at 200 ℃, cooling, and taking out for later use;
(4) Taking 461.5mg of PbI 2 142.8mg of FAI (1H-imidazol-1-yl (2-methyl-3-furan)Based) methanone) dissolved in 90ul of the mixed solvent system of example 3, DIO (1, 8-diiodooctane) added with PbI 2 The molar ratio of (1) to (2) is 0.65, and the total concentration of solute in the solution is 1.12mol/ml.
(5) SnO obtained in step (3) 2 Spin coating the perovskite precursor solution of the step (4) on the electron transport layer: the whole spin coating process is divided into three steps, firstly spin coating for 5 seconds at 5000 rpm/min; then spin-coating at 6000rpm/min for 30 seconds; the thickness of the obtained perovskite light absorption layer is controlled to be about 600 nm;
(6) Annealing the assembly obtained in the step (5) at 70 ℃ for 10 minutes in a nitrogen environment, cooling, and taking out the assembly in an air environment with the humidity of 45%;
(7) Transferring the assembly prepared in the step (6) into a glove box in a nitrogen environment, mixing 54.75mg of Spiro-OMeTAD with 750ul of CBZ, 13.5ul of Li-TFSI, 21.75ul of FK209 and 22.5ul of TBP, and spin-coating at 4000rpm for 30s to obtain a hole transport layer;
(8) The assembly prepared in the step (7) is also used for preparing a gold electrode by adopting a thermal evaporation deposition method, and the vacuum degree is controlled to be lower than 4 x 10 -4 Pa, the evaporation rate is 1-2 angstroms/second, and the thickness of the gold electrode is 100nm, so that the perovskite solar cell device is prepared.
Example 10
(1) Cleaning the FTO glass etched and processed by the femtosecond laser by the method, and carrying out UVO treatment for 15 minutes for later use;
(2) Preparing SnO with the thickness of 20nm by using the treated FTO glass through a CBD (chemical bath deposition) process 2 An electron transport layer;
(3) Coated SnO 2 Placing the FTO glass of the electron transmission layer into a titanium-based heating table, annealing for 60 minutes at 200 ℃, cooling, and taking out for later use;
(4) Taking 461.5mg of PbI 2 142.8mg of FAI (1H-imidazol-1-yl (2-methyl-3-furanyl) methanone) dissolved in 90ul of the mixed solvent system of example 4, DIO (1, 8-diiodooctane) added in an amount corresponding to PbI 2 The molar ratio of (1) is 0.65, and the total concentration of solute in the solution is 1.12mol/ml.
(5) SnO obtained in step (3) 2 Spin coating the perovskite precursor solution of the step (4) on the electron transport layer:the whole spin coating process is divided into three steps, firstly spin coating for 5 seconds at 5000 rpm/min; then spin-coating at 6000rpm/min for 30 seconds; the thickness of the obtained perovskite light absorption layer is controlled to be about 600 nm;
(6) Annealing the component obtained in the step (5) at 70 ℃ for 10 minutes in a nitrogen environment, cooling and taking out the component in an air environment with the humidity of 45%;
(7) Transferring the assembly prepared in the step (6) into a glove box in a nitrogen environment, mixing 54.75mg of Spiro-OMeTAD with 750ul of CBZ, 13.5ul of Li-TFSI, 21.75ul of FK209 and 22.5ul of TBP, and spin-coating at 4000rpm for 30s to obtain a hole transport layer;
(8) The assembly prepared in the step (7) is also used for preparing a gold electrode by adopting a thermal evaporation deposition method, and the vacuum degree is controlled to be lower than 4 x 10 -4 Pa, the evaporation rate is 1-2 angstroms/second, and the thickness of the gold electrode is 100nm, so that the perovskite solar cell device is prepared.
Example 11
(1) Cleaning the FTO glass etched and processed by the femtosecond laser by the method, and carrying out UVO treatment for 15 minutes for later use;
(2) Preparing SnO with the thickness of 20nm by the treated FTO glass through a CBD (chemical water bath deposition) process 2 An electron transport layer;
(3) Coated SnO 2 Placing the FTO glass of the electron transmission layer into a titanium-based heating table, annealing for 60 minutes at 200 ℃, cooling, and taking out for later use;
(4) Taking 461.5mg of PbI 2 142.8mg of FAI (1H-imidazol-1-yl (2-methyl-3-furanyl) methanone), dissolved in 90ul of the mixed solvent system of example 5, with a molar ratio of DIO added to PbI2 of 0.65.
(5) SnO obtained in step (3) 2 Spin coating the perovskite precursor solution of the step (4) on the electron transport layer: the whole spin coating process is divided into three steps, firstly spin coating for 5 seconds at 5000 rpm/min; then spin-coating at 6000rpm/min for 30 seconds; the thickness of the obtained perovskite light absorption layer is controlled to be about 600 nm;
(6) Annealing the assembly obtained in the step (5) at 70 ℃ for 10 minutes in a nitrogen environment, cooling, and taking out the assembly in an air environment with the humidity of 45%;
(7) Transferring the assembly prepared in the step (6) into a glove box in a nitrogen environment, mixing 54.75mg of Spiro-OMeTAD with 750ul of CBZ, 13.5ul of Li-TFSI, 21.75ul of FK209 and 22.5ul of TBP, and spin-coating at 4000rpm for 30s to obtain a hole transport layer;
(8) The assembly prepared in the step (7) is also used for preparing a gold electrode by adopting a thermal evaporation deposition method, and the vacuum degree is controlled to be lower than 4 x 10 -4 Pa, the evaporation rate is 1-2 angstroms/second, and the thickness of the gold electrode is 100nm, so that the perovskite solar cell device is prepared.
Example 12
(1) Cleaning the FTO glass etched and processed by the femtosecond laser by the method, and then carrying out UVO treatment for 15 minutes for later use;
(2) Preparing SnO with the thickness of 20nm by the treated FTO glass through a CBD (chemical water bath deposition) process 2 An electron transport layer;
(3) Coated SnO 2 Placing the FTO glass of the electron transmission layer into a titanium-based heating table, annealing for 60 minutes at 200 ℃, cooling, and taking out for later use;
(4) Taking 461.5mg of PbI 2 142.8mg of FAI (1H-imidazol-1-yl (2-methyl-3-furanyl) methanone) dissolved in 90. Mu.l of the mixed solvent system of example 6, DIO (1, 8-diiodooctane) added in an amount corresponding to that of PbI 2 The molar ratio of (1) is 0.65, and the total concentration of solute in the solution is 1.12mol/ml.
(5) SnO obtained in step (3) 2 Spin-coating the perovskite precursor solution obtained in the step (4) on an electron transport layer: the whole spin coating process is divided into three steps, firstly spin coating for 5 seconds at 5000 rpm/min; then spin-coating at 6000rpm/min for 30 seconds; the thickness of the obtained perovskite light absorption layer is controlled to be about 600 nm;
(6) Annealing the assembly obtained in the step (5) at 70 ℃ for 10 minutes in a nitrogen environment, cooling, and taking out the assembly in an air environment with the humidity of 45%;
(7) Transferring the assembly prepared in the step (6) into a glove box in a nitrogen environment, mixing 54.75mg of Spiro-OMeTAD with 750ul of CBZ, 13.5ul of Li-TFSI, 21.75ul of FK209 and 22.5ul of TBP, and spin-coating at 4000rpm for 30s to obtain a hole transport layer;
(8) The assembly prepared in the step (7) is also used for preparing a gold electrode by a thermal evaporation deposition method and controllingVacuum degree lower than 4 x 10 -4 Pa, the evaporation rate is 1-2 angstroms/second, and the thickness of the gold electrode is 100nm, so that the perovskite solar cell device is prepared.
Example 13
(1) Cleaning the FTO glass etched and processed by the femtosecond laser by the method, and then carrying out UVO treatment for 15 minutes for later use;
(2) Preparing SnO with the thickness of 20nm by the treated FTO glass through a CBD (chemical water bath deposition) process 2 An electron transport layer;
(3) Coated SnO 2 Placing the FTO glass of the electron transmission layer into a titanium-based heating table, annealing for 60 minutes at 200 ℃, cooling, and taking out for later use;
(4) Taking 461.5mg of PbI 2 142.8mg of FAI (1H-imidazol-1-yl (2-methyl-3-furanyl) methanone) dissolved in 90ul of the mixed solvent system of example 6, the amount of chloroisooctane added and PbI 2 The molar ratio of (1) is 0.65, and the total concentration of solute in the solution is 1.12mol/ml.
(5) SnO obtained in step (3) 2 Spin-coating the perovskite precursor solution obtained in the step (4) on an electron transport layer: the whole spin coating process is divided into three steps, firstly spin coating for 5 seconds at 5000 rpm/min; then spin-coating at 6000rpm/min for 30 seconds; the thickness of the obtained perovskite light absorption layer is controlled to be about 600 nm;
(6) Annealing the component obtained in the step (5) at 70 ℃ for 10 minutes in a nitrogen environment, cooling and taking out the component in an air environment with the humidity of 45%;
(7) Transferring the assembly prepared in the step (6) into a glove box in a nitrogen environment, mixing 54.75mg of Spiro-OMeTAD with 750ul of CBZ, 13.5ul of Li-TFSI, 21.75ul of FK209 and 22.5ul of TBP, and spin-coating at 4000rpm for 30s to obtain a hole transport layer;
(8) The assembly prepared in the step (7) is also used for preparing a gold electrode by adopting a thermal evaporation deposition method, and the vacuum degree is controlled to be lower than 4 x 10 -4 Pa, the evaporation rate is 1-2 angstroms/second, and the thickness of the gold electrode is 100nm, so that the perovskite solar cell device is prepared.
Comparative example 1
(1) Cleaning the FTO glass etched and processed by the femtosecond laser by the method, and carrying out UVO treatment for 15 minutes for later use;
(2) Preparing SnO with the thickness of 20nm by the treated FTO glass through a CBD (chemical water bath deposition) process 2 An electron transport layer;
(3) Coated SnO 2 Placing the FTO glass of the electron transmission layer into a titanium-based heating table, annealing for 60 minutes at 200 ℃, cooling, and taking out for later use;
(4) Taking 461.5mg of PbI 2 142.8mg of FAI and 90ul of NMP are dissolved in DMF solvent, and the solution is stirred at normal temperature overnight to obtain perovskite precursor solution, wherein the total concentration of solute in the solution is 1.12mol/ml.
(5) SnO obtained in step (3) 2 Spin-coating the perovskite precursor solution obtained in the step (4) on an electron transport layer: the whole spin coating process is divided into three steps, firstly spin coating for 5 seconds at 5000 rpm/min; then spin-coating at 6000rpm/min for 30 seconds; the thickness of the obtained perovskite light absorption layer is controlled to be about 600 nm;
(6) Annealing the component obtained in the step (5) at 70 ℃ for 10 minutes in a nitrogen environment, cooling and taking out the component in an air environment with the humidity of 45%;
(7) Transferring the assembly prepared in the step (6) into a glove box in a nitrogen environment, mixing 54.75mg of Spiro-OMeTAD with 750ul of CBZ, 13.5ul of Li-TFSI, 21.75ul of FK209 and 22.5ul of TBP, and spin-coating at 4000rpm for 30s to obtain a hole transport layer;
(8) The assembly prepared in the step (7) is also used for preparing a gold electrode by adopting a thermal evaporation deposition method, and the vacuum degree is controlled to be lower than 4 x 10 -4 Pa, the evaporation rate is 1-2 angstroms/second, and the thickness of the gold electrode is 100nm, so that the perovskite solar cell device is prepared.
Test method and results
And (3) testing the battery performance: the perovskite solar cell prepared in the above example was tested at a standard solar intensity (am1.5g, 100mW/cm 2) using a solar simulator (xenon lamp as light source) calibrated using a silicon diode (with KG9 visible filter) in the us national renewable energy laboratory. The corresponding test results are shown in table 1 and fig. 2.
Table 1 perovskite solar cell performance parameter table prepared according to different embodiments
From the battery performance test data, it can be seen that: the perovskite solar cell based on the solvent system is superior to the perovskite solar cell prepared based on the conventional solvent in photoelectric conversion efficiency; furthermore, the perovskite solar cell with higher efficiency can be obtained by regulating and controlling the proportion of each solvent in the novel solvent system.
The above are only preferred embodiments of the present invention, and do not limit the scope of the present invention, and it is obvious to those skilled in the art that various modifications and variations can be made in the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the scope of the present invention.
Claims (10)
1. A mixed solvent system for addition to a perovskite precursor solution, the mixed solvent system comprising the following raw materials: chloroisooctane, N-ethyl-2-pyrrolidone and dimethyl sulfoxide.
2. The mixed solvent system according to claim 1, wherein the volume ratio of the dimethylsulfoxide and the N-ethyl-2-pyrrolidone is 0.3.
3. The mixed solvent system according to claim 2, wherein the volume ratio of the dimethylsulfoxide and the N-ethyl-2-pyrrolidone is 0.3.
4. The mixed solvent system according to claim 1, wherein the ratio of the total number of moles of the chloroisooctane, the N-ethyl-2-pyrrolidone and the number of moles of Pb ions in the perovskite precursor solution is from 0.5 to 1.8.
5. A perovskite active layer formed by adding the mixed solvent system as defined in any one of claims 1 to 4 to a perovskite precursor solution and applying the perovskite precursor solution to an electron transport layer.
6. The perovskite active layer of claim 5, wherein the thickness of the perovskite active layer is from 100 to 1000nm.
7. A preparation method of a perovskite active layer is characterized by comprising the following steps:
providing a mixed solvent system according to any one of claims 1 to 4, mixing the mixed solvent system with a perovskite precursor solution to prepare a precursor solution;
and dropwise adding the precursor onto the surface of the electron transport layer, and spin-coating to prepare a film to obtain the perovskite active layer.
8. A perovskite solar cell comprising the perovskite active layer as claimed in any one of claims 5 to 6.
9. The perovskite solar cell according to claim 8, comprising an electrically conductive glass substrate, an electron transport layer, a hole transport layer and a metal electrode in sequential overlying arrangement, the perovskite active layer being disposed between the electron transport layer and the hole transport layer.
10. A preparation method of a perovskite solar cell is characterized by comprising the following steps:
cleaning a substrate;
preparing a hole transport layer;
preparing a precursor solution of the perovskite active layer;
preparing a perovskite active layer;
preparing an electron transport layer;
and (5) evaporating the metal electrode.
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