CN114156412B - Application of potassium salt containing large-size strong coordination organic anion in perovskite solar cell - Google Patents

Application of potassium salt containing large-size strong coordination organic anion in perovskite solar cell Download PDF

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CN114156412B
CN114156412B CN202111490932.5A CN202111490932A CN114156412B CN 114156412 B CN114156412 B CN 114156412B CN 202111490932 A CN202111490932 A CN 202111490932A CN 114156412 B CN114156412 B CN 114156412B
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陈江照
白乐
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Chongqing University
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Abstract

The invention relates to application of potassium salt containing large-size strong coordination organic anions in a perovskite solar cell, belonging to the technical field of perovskite preparation. The invention uses large-size strong coordination organic anion potassium salt which contains carboxyl and sulfonic group and can generate strong coordination with uncoordinated lead ions to prepare the perovskite solar cell. Because of the sulfonic acid functional group and the carboxyl functional group of the large-size strong coordination organic anion can be combined with the uncoordinated lead ion Pb 2+ And/or the halogen vacancies are subjected to strong coordination interaction, so that the perovskite solar cell is firmly anchored in the perovskite solar cell crystal boundary, the crystal boundary ion migration and the crystal boundary defect passivation are synergistically inhibited, the perovskite solar cell is effectively inhibited from being subjected to phase separation, the carrier mobility is obviously increased, the carrier life of the perovskite thin film is prolonged, and meanwhile, the non-radiative recombination of the carriers at the interface is greatly reduced, so that the power conversion efficiency and the long-term stability of the perovskite solar cell are improved, and the effective method for efficiently stabilizing the perovskite solar cell is provided.

Description

Application of potassium salt containing large-size strong coordination organic anion in perovskite solar cell
Technical Field
The invention belongs to the technical field of perovskite preparation, and relates to application of potassium salt containing large-size strong coordination organic anions in a perovskite solar cell, the perovskite solar cell containing the large-size strong coordination organic anion potassium salt and a preparation method thereof.
Background
Perovskite Solar Cells (PSCs) have become the fastest developing solar cell technology due to their advantages of low cost, adjustable band gap, long carrier diffusion length, high molar absorption coefficient, solution processible, flexibility, high Power Conversion Efficiency (PCE), and the like, and have received extensive attention from both academic and industrial circles. To date, unijunction PSCs have achieved a 25.5% record authentication efficiency. Although PSCs have achieved higher PCEs, their long-term stability has always faced significant challenges that have hindered their commercial application.
It is well known that polycrystalline perovskite thin films rapidly crystallize and grow during high temperature annealing, inevitably accompanied by the generation of a large number of defects which hinder carrier transport, transfer and extraction, resulting in severe bulk and interface non-radiative recombination. It has been experimentally and theoretically demonstrated that vacancy defects (particularly halogen vacancies) are most easily formed among all point defects because their formation energy is lowest; when it migrates to the grain boundaries, it will become the carrier recombination center. In addition, these halogen ion vacancies will act as a channel for halogen ion migration, which will result in charge accumulation at the grain boundaries and/or interfaces, resulting in a decrease in the photovoltaic performance of the device. Charge accumulation and interfacial capacitance due to ion migration are reported to be the main causes of the lag in perovskite solar cells. Furthermore, halogen ion migration in mixed-halogen perovskite thin films can lead to perovskite phase separation, which is one of the main reasons for poor long-term device stability. Therefore, it is urgently required to inhibit ion migration by passivating vacancy defects, thereby blocking ion migration pathway channels.
Although compositional and solvent engineering have been developed to produce high quality perovskite thin films to inhibit the formation of defects in polycrystalline perovskite thin films, the formation of defects is not completely avoidable. Additive engineering is a well-recognized and very effective perovskite grain boundary defect passivation strategy. To date, a variety of additive molecules have been explored to passivate defects in perovskite films, such as lewis acids, lewis bases, organic/inorganic salts, and the like. In the past years, potassium ion (K) + ) Has been shown to effectively passivate defects and inhibit or eliminate hysteresis. However, the reported potassium salt additive molecules typically employ inorganic anions such as halide anions, hexafluorophosphate, sulfate, and the like. However, these inorganic anions are still susceptible to migration because their ionic radius is still similar to that of the halide ion. Generally, anions can interact with perovskites through ionic bonds, so enhancing the interaction between the anion and the perovskite will facilitate passivation of defects and inhibition of ion migration. In view of this, it is possible to combine a functional group having a strong coordinating ability (for example, carboxylic acid (-COOH)) and sulfonic acid (-SO) 3 H) Large size organic anions are designed.
In view of this, passivation of grain boundary defects and inhibition of ion migration by using a composition containing a large-sized organic anion are important for reducing or eliminating hysteresis, improving efficiency and stability of a battery.
Disclosure of Invention
In view of the above, it is an object of the present invention to provide a use of a potassium salt containing a large-sized strongly coordinating organic anion in a perovskite solar cell; the second purpose of the invention is to provide a perovskite solar cell containing large-size strongly coordinated organic anion sylvite; the invention also aims to provide a preparation method of the perovskite solar cell containing the large-size strong coordination organic anion potassium salt.
In order to achieve the purpose, the invention provides the following technical scheme:
1. the application of potassium salt containing large-size strongly-coordinated organic anions in perovskite solar cells is characterized in that the large-size strongly-coordinated organic anions in the potassium salt containing the large-size strongly-coordinated organic anions contain carboxyl and sulfonic acid groups, and the large-size strongly-coordinated organic anions can generate strong coordination with uncoordinated lead ions.
Preferably, the application specifically comprises: salts containing large-size strongly coordinating organic anions are added to perovskite light-absorbing layers of Perovskite Solar Cells (PSCs) for modifying the perovskite light-absorbing layers.
Preferably, the potassium salt containing a large-size strongly coordinating organic anion is 4-sulfobenzoic acid monopotassium salt.
2. The perovskite solar cell comprises a perovskite light absorption layer containing large-size strong coordination organic anion sylvite.
Preferably, the large-size strong coordination organic anion potassium salt is 4-sulfobenzoic acid monopotassium salt.
Further preferably, the perovskite solar cell comprises, from bottom to top, an electrically conductive substrate layer, an Electron Transport Layer (ETL), a perovskite light absorbing layer containing a large-size strongly coordinating organic anion potassium salt, a Hole Transport Layer (HTL) and a metal back electrode.
Further preferably, the conductive substrate layer is ITO conductive glass or FTO conductive glass;
the material of the Electron Transport Layer (ETL) is any one or more of tin dioxide, titanium dioxide, zinc oxide, barium stannate or cerium dioxide;
the Hole Transport Layer (HTL) is made of any one or more of 2,2',7,7' -tetra [ N, N-di (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-OMeTAD), poly [ bis (4-phenyl) (2,4,6-trimethylphenyl) amine ] (PTAA), poly (3-hexylthiophene-2,5-diyl) (P3 HT), cuprous thiocyanate (CuSCN), cuprous iodide (CuI) or nickel oxide (NiO);
the metal back electrode is made of any one of gold, silver, aluminum or low-temperature carbon.
Further preferably, the material of the perovskite light absorption layer further comprises ABX 3 Wherein A is CH 3 NH 3 + 、CH(NH 2 ) 2 + 、Cs + Or Rb + B is Pb 2+ 、Sn 2+ Or Ge 2+ At least one of (1), X is Cl - 、Br - Or I - At least one of (a).
3. The preparation method of the perovskite solar cell comprises the following steps:
(1) Preparation of Electron Transport Layer (ETL): dropwise adding a solution containing an Electron Transport Layer (ETL) material onto a pretreated conductive substrate, spin-coating, annealing, and then performing ultraviolet ozone irradiation or Plasma treatment to form an Electron Transport Layer (ETL) on the conductive substrate;
(2) Preparing a perovskite light absorption layer: spin-coating a perovskite precursor solution containing a sylvite of large-size strongly-coordinated organic anions and a perovskite light absorption layer material on the Electron Transport Layer (ETL) prepared in the step (1), dropwise adding an anti-solvent, annealing, and preparing a perovskite light absorption layer on the Electron Transport Layer (ETL);
(3) Preparation of Hole Transport Layer (HTL): dropwise adding a solution containing a Hole Transport Layer (HTL) material on the perovskite light absorption layer prepared in the step (3), and performing spin coating to prepare a Hole Transport Layer (HTL) on the perovskite light absorption layer;
(4) Preparing a metal back electrode: and (4) preparing a metal back electrode on the Hole Transport Layer (HTL) prepared in the step (4) by adopting a thermal evaporation method.
Preferably, the pretreatment is: sequentially ultrasonically cleaning the conductive substrate by using a detergent, deionized water, acetone and absolute ethyl alcohol, blow-drying the conductive substrate by using nitrogen, carrying out ultraviolet ozone treatment on the conductive substrate, and cooling the conductive substrate;
the concentration of lead ions in the perovskite precursor solution is 0.5-2.5 mol/L, the concentration of large-size strongly-coordinated organic anion sylvite in the perovskite precursor solution is 0.01-5.0 mg/mL, and the solvent in the perovskite precursor solution is one or two of N, N-dimethylformamide or dimethyl sulfoxide;
the spin coating specifically comprises the following steps: the rotating speed is 2000-6000 rpm, and the spin coating time is 20-60 s;
the annealing specifically comprises the following steps: the temperature is 100-200 ℃, and the annealing time is 10-60 min;
the anti-solvent is any one or more of dichloromethane, dichlorobenzene, toluene, ethyl acetate, chloroform, diethyl ether or chlorobenzene.
The invention has the beneficial effects that:
1. the invention discloses application of potassium salt containing large-size strong coordination organic anions in a perovskite solar cell, namely, the potassium salt containing large-size strong coordination organic anions, which contain carboxyl and sulfonic groups and can generate strong coordination with uncoordinated lead ions, is used for preparing the perovskite solar cell. Because the large-size strong coordination organic anion potassium salt contains sulfonic acid functional group and carboxyl functional group which can be combined with uncoordinated lead ion Pb 2+ And/or the halogen vacancy has strong coordination interaction, so that the perovskite solar cell is firmly anchored in the crystal boundary of the perovskite solar cell, the crystal boundary ion migration and the crystal boundary defect passivation are synergistically inhibited, the perovskite solar cell is effectively inhibited from being separated, the carrier mobility is obviously increased, the carrier service life of a perovskite film is prolonged, meanwhile, the non-radiative recombination of carriers at the interface is greatly reduced, the power conversion efficiency and the long-term stability of the perovskite solar cell are improved, and the perovskite solar cell is effectively, efficiently and stably providedThe method of (1).
2. The invention also discloses a perovskite solar cell containing large-size strong coordination organic anions, wherein the perovskite light absorption layer in the perovskite solar cell contains the large-size strong coordination organic anions, the service life of a perovskite film carrier is prolonged to 2.06 mu s, and the perovskite film carrier has the highest power conversion efficiency of 22.68 percent; meanwhile, the unencapsulated perovskite solar cell has excellent long-term stability (the perovskite solar cell can maintain 98% of the initial efficiency after being placed in an environment with the relative humidity of 20-30% for 1320h, and can maintain 99% of the initial efficiency after being placed in an environment with the temperature of 60 ℃ for 1320 h). Therefore, the perovskite solar cell containing the large-size strong coordination organic anion potassium salt disclosed by the invention has very important significance for promoting the commercialization process of the perovskite solar cell.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims thereof.
Drawings
For a better understanding of the objects, aspects and advantages of the present invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 shows 4-sulfobenzoic acid monopotassium salt molecule and FAPbI 3 A is a schematic diagram of several interaction modes of formamidine hydroiodide, lead iodide and 4-sulfobenzoic acid monopotassium salt in perovskite components (FAI-I-FAI-VI is six different interaction modes between 4-sulfobenzoic acid monopotassium salt molecules and formamidine hydroiodide, pbI 2 -I～PbI 2 -VI is respectively 4-sulfobenzoic acid monopotassium salt molecule and PbI 2 Six different modes of action); b is the formation energy of several cases shown in a in figure 1 calculated according to DFT; c is a state density calculation result chart of a plurality of interaction modes shown in a in figure 1 (perovskite is perovskite)The SAMS-PVSK is perovskite containing 4-sulfobenzoic acid monopotassium salt molecules, and the 4-SBA is 4-sulfobenzoate radical anion);
FIG. 2 is an X-ray photoelectron spectroscopy (XPS) chart of 4-sulfobenzoic acid monopotassium salt molecules (SAMS), the perovskite solar cell light-absorbing layer prepared in comparative example without 4-sulfobenzoic acid monopotassium salt molecules (comparative example), the perovskite solar cell light-absorbing layer containing 4-sulfobenzoic acid monopotassium salt molecules in example 1 (example 1);
FIG. 3 is a mixture of 4-sulfobenzoic acid monopotassium salt molecule (SAMS), lead iodide and 4-sulfobenzoic acid monopotassium salt (PbI) 2 + SAMS), perovskite solar cell light-absorbing layer containing no 4-sulfobenzoic acid monopotassium salt molecule in comparative example (comparative example), perovskite solar cell light-absorbing layer containing 4-sulfobenzoic acid monopotassium salt molecule in example 1 (example 1) 13 C nuclear magnetic resonance spectrogram;
FIG. 4 is a time-of-flight secondary ion mass spectrum of a perovskite solar cell not containing a single potassium salt molecule of 4-sulfobenzoic acid in comparative example (comparative example) and a perovskite solar cell containing a single potassium salt molecule of 4-sulfobenzoic acid in example 1 (example 1), wherein fresh samples refer to perovskite solar cells that have not been illuminated as prepared;
FIG. 5 is a time resolved microwave conductivity test plot for the light absorbing layers of perovskite solar cells prepared in comparative example and example 1;
FIG. 6 is a Time Resolved Photoluminescence (TRPL) spectrum of a light absorbing layer of a perovskite solar cell prepared in comparative example and example 1 measured under 468nm excitation conditions;
FIG. 7 shows perovskite solar cells in comparative example and example 1 at 100mW/cm 2 Under the sunlight simulation light source, the positive scanning current density-voltage (J-V) curve graph and the reverse scanning current density-voltage (J-V) curve graph are measured at the scanning speed of 50 mV/S;
FIG. 8 is a graph of the results of the humidity stability test of the unencapsulated perovskite solar cell in comparative example and example 1, when placed continuously in air at 20-30% relative humidity;
fig. 9 is a graph showing the results of thermal stability tests conducted on the unencapsulated perovskite solar cell in comparative example and example 1, when the cell was continuously placed in a nitrogen atmosphere at 60 ℃.
Detailed Description
The following embodiments of the present invention are provided by way of specific examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It should be noted that the drawings provided in the following embodiments are only for illustrating the basic idea of the present invention in a schematic way, and the features in the following embodiments and examples may be combined with each other without conflict.
Example 1
A perovskite solar cell containing large-size strongly coordinated organic anion sylvite is prepared by the following specific steps:
(1) Pretreating the conductive substrate: selecting ITO transparent conductive glass with a resistance of 15 ohms as a conductive substrate, sequentially ultrasonically cleaning the conductive substrate with a detergent, deionized water (with a resistivity of more than 10M omega), acetone and absolute ethyl alcohol for 20min, then blowing nitrogen to be completely dried, placing the conductive substrate in an ultraviolet ozone cleaning machine for ultraviolet ozone treatment for 15min, and cooling the conductive substrate to room temperature to obtain the pretreated conductive substrate.
(2) Preparation of Electron Transport Layer (ETL): 40 μ L of a solution containing an Electron Transport Layer (ETL) material (250 μ L of SnO with a mass fraction of 15% 2 Adding 750 μ L deionized water into the nanoparticle dispersion, shaking the solution for 5min, performing ultrasonic treatment for 10min, and filtering with 0.22 μm PVDF membrane), adding into the pretreated conductive substrate, starting spin coater for spin coating (the rotation speed of the spin coater is 3000rpm, and the spin coating time is 30 s), annealing (the temperature is set to 150 deg.C, and the temperature is kept stable for 30 min),then, ultraviolet ozone irradiation was performed for 15min to form an Electron Transport Layer (ETL) on the conductive substrate.
(3) Preparing a perovskite light absorption layer: under a low humidity environment (10-20% relative humidity), 40 μ L of perovskite precursor solution containing 4-sulfobenzoic acid monopotassium salt and perovskite light-absorbing layer material (0.5mg of 4-sulfobenzoic acid monopotassium salt (0.025 mmol), 248.16mg formamidine hydroiodide (1.443 mmol), 19.73mg of CsI (0.076 mmol), 6.58mg of RbI (0.031 mmol), 682.73mg of PbI 2 (1.481mmol)、8.53mg PbBr 2 (0.023mmol)、12.74mg PbCl 2 (0.046 mmol) and 35mg of methylamine hydrochloride (0.518 mmol) are dissolved in a mixed solvent of N, N-dimethylformamide (800 muL) and dimethyl sulfoxide (200 muL), the solution is shaken for 10min and subjected to ultrasound for 10min to prepare 1.55mol/L of perovskite precursor solution, the perovskite precursor solution is dropwise added on the Electron Transport Layer (ETL) prepared in the step (2), after the solution is uniformly distributed on the Electron Transport Layer (ETL), a spin coater is started to spin-coat for 30s at the rotation speed of 4000rpm, 80 muL of chlorobenzene is dropwise added in 15-16 s before the spin coating is finished, then annealing is carried out (a hot stage is started in advance, the temperature is set to 130 ℃, after the temperature of the hot stage is raised to 130 ℃ and stabilized, the substrate of the perovskite layer is placed on the hot stage to be annealed, the temperature of the hot stage is kept stable in the annealing process, and the substrate is taken down after 30min, namely, the light absorption layer can be prepared on the Electron Transport Layer (ETL).
(4) Preparation of Hole Transport Layer (HTL): mu.L of a solution containing a Hole Transport Layer (HTL) material (72.3 mg of 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-OMeTAD) was dissolved in lmL chlorobenzene, and 29. Mu.L of 4-tert-butylpyridine and 18. Mu.L of a lithium bistrifluoromethanesulfonylimide solution (concentration 520mg/mL, solvent anhydrous acetonitrile) were added, shaken for 5min, sonicated for 10min, filtered through a 0.22. Mu.m PTFE film) were dropped on the perovskite light absorbing layer prepared in step (3), a spin coater was started, spin-coated (rotation speed set at 4000rpm, time set at 30 s) to prepare a Hole Transport Layer (HTL) on the perovskite light absorbing layer.
(5) Preparing a metal back electrode: setting the pressure of the vapor deposition instrument to 1 × 10 -4 Pa, on the hole transport layer prepared in step (4) by thermal evaporation, first
Figure BDA0003399315570000061
In (b) is evaporated with 10nm Au and then combined with->
Figure BDA0003399315570000062
And depositing 70nm Au at the speed of the above step to finally prepare an Au electrode with the thickness of 80nm, namely forming a metal back electrode on a Hole Transport Layer (HTL) to obtain the perovskite solar cell containing the large-size strong coordination organic anion sylvite.
Example 2
A perovskite solar cell containing large-size strongly coordinated organic anion sylvite is prepared by the following specific steps:
(1) Pretreating the conductive substrate: selecting FTO transparent conductive glass with the resistance of 15 ohms as a conductive substrate, sequentially ultrasonically cleaning the conductive substrate with a detergent, deionized water (the resistivity is more than 10M omega), acetone and absolute ethyl alcohol for 20min, then blowing nitrogen to be completely dried, placing the conductive substrate in an ultraviolet ozone cleaning machine for ultraviolet ozone treatment for 10min, and cooling the conductive substrate to room temperature to obtain the pretreated conductive substrate.
(2) Preparation of Electron Transport Layer (ETL): firstly, tiCl is added 4 Mixing with deionized water in ice bath to prepare TiCl 4 The solution was stored in a refrigerator at-4 ℃. Then soaking the pretreated FTO in 0.18mol/L TiCl for a short time 4 After being in solution, the solution was placed in a sealed glass container. Then the glass container is put into a drying oven, the temperature is set to 70 ℃, and the glass container is taken out after 45 minutes and cooled. Repeatedly washing the FTO substrate with ethanol and deionized water for three times to remove surface residues, then annealing at 200 ℃ for 1 hour, cooling to room temperature to obtain TiO 2 An Electron Transport Layer (ETL).
(3) Preparing a perovskite light absorption layer: firstly, the substrate of the prepared electron transport layer is treated by ultraviolet-ozone for 30min. Under a low humidity environment (10-20% relative humidity), 40 μ L of perovskite precursor solution containing 4-sulfobenzoic acid monopotassium salt and perovskite light-absorbing layer material (0.5mg of 4-sulfobenzoic acid monopotassium salt (0.025 mmol), 248.16mg of formamidine hydroiodide (1.443 mmol), 19.73mg of CsI (0.076 m)mol)、6.58mg RbI(0.031mmol)、682.73mg PbI 2 (1.481mmol)、8.53mg PbBr 2 (0.023mmol)、12.74mg PbCl 2 (0.046 mmol) and 35mg of methylamine hydrochloride (0.518 mmol) are dissolved in a mixed solvent of N, N-dimethylformamide (800 muL) and dimethyl sulfoxide (200 muL), the solution is shaken for 10min and subjected to ultrasound for 10min to prepare 1.55mol/L of perovskite precursor solution, the perovskite precursor solution is dropwise added on the Electron Transport Layer (ETL) prepared in the step (2), after the solution is uniformly distributed on the Electron Transport Layer (ETL), a spin coater is started to spin-coat for 30s at the rotation speed of 4000rpm, 80 muL of chlorobenzene is dropwise added in 15-16 s before the spin coating is finished, then annealing is carried out (a hot stage is started in advance, the temperature is set to 150 ℃, after the temperature of the hot stage is raised to 150 ℃ and stabilized, the substrate of the perovskite layer is placed on the hot stage to be annealed, the temperature of the hot stage is kept stable in the annealing process, and the substrate is taken down after 30min, and then the light absorption layer can be prepared on the Electron Transport Layer (ETL).
(4) Preparation of Hole Transport Layer (HTL): mu.L of a solution containing a Hole Transport Layer (HTL) material (72.3 mg of 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-OMeTAD) was dissolved in lmL chlorobenzene, and 29. Mu.L of 4-tert-butylpyridine and 18. Mu.L of a lithium bistrifluoromethanesulfonylimide solution (concentration 520mg/mL, solvent anhydrous acetonitrile) were added, shaken for 5min, sonicated for 10min, filtered through a 0.22. Mu.m PTFE film) were dropped on the perovskite light absorbing layer prepared in step (3), a spin coater was started, spin-coated (rotation speed set at 4000rpm, time set at 30 s) to prepare a Hole Transport Layer (HTL) on the perovskite light absorbing layer.
(5) Preparing a metal back electrode: setting the pressure of the vapor deposition instrument to 1 × 10 -4 Pa, on the hole transport layer prepared in step (4) by thermal evaporation, first
Figure BDA0003399315570000071
At a speed of 10nm and then based on ^ 4>
Figure BDA0003399315570000072
The silver is evaporated at a speed of 90nm to finally prepare a silver electrode with a thickness of 100nm, namely a metal back electrode can be formed on a Hole Transport Layer (HTL) so as to obtain a silver electrode with large size and strong strengthA perovskite solar cell coordinated with an organic anion potassium salt.
Example 3
A perovskite solar cell containing large-size strongly coordinated organic anion sylvite is prepared by the following specific steps:
(1) Pretreating the conductive substrate: selecting ITO transparent conductive glass with the resistance of 15 ohms as a conductive substrate, sequentially ultrasonically cleaning the conductive substrate with a detergent, deionized water (the resistivity is more than 10M omega), acetone and absolute ethyl alcohol for 20min, then blowing nitrogen to be completely dried, placing the conductive substrate in an ultraviolet ozone cleaning machine for ultraviolet ozone treatment for 5min, and cooling the conductive substrate to room temperature to obtain the pretreated conductive substrate.
(2) Preparation of Electron Transport Layer (ETL): firstly TiCl is added 4 Mixing with deionized water in ice bath to prepare TiCl 4 The solution was stored in a refrigerator at-4 ℃. Then soaking the pretreated FTO in 0.18mol/L TiCl for a short time 4 After being in solution, the solution was placed in a sealed glass container. Then the glass container is put into a drying oven, the temperature is set to 70 ℃, and the glass container is taken out after 45 minutes and cooled. Repeatedly washing the FTO substrate with ethanol and deionized water for three times to remove surface residues, then annealing at 200 ℃ for 1 hour, cooling to room temperature to obtain TiO 2 An Electron Transport Layer (ETL).
(3) Preparing a perovskite light absorption layer: firstly, the substrate of the prepared electron transport layer is treated by ultraviolet-ozone for 30min. Under a low humidity environment (10-20% relative humidity), 40. Mu.L of perovskite precursor solution containing 4-sulfobenzoic acid monopotassium salt and perovskite light-absorbing layer material (0.5mg of 4-sulfobenzoic acid monopotassium salt (0.025 mmol), 248.16mg formamidine hydroiodide (1.443 mmol), 19.73mg CsI (0.076 mmol), 6.58mg RbI (0.031 mmol), 682.73mg PbI 2 (1.481mmol)、8.53mg PbBr 2 (0.023mmol)、12.74mg PbCl 2 (0.046 mmol) and 35mg of methylamine hydrochloride (0.518 mmol) are dissolved in a mixed solvent of N, N-dimethylformamide (800 mu L) and dimethyl sulfoxide (200 mu L), the mixture is shaken for 10min and subjected to ultrasound for 10min to prepare 1.55mol/L of perovskite precursor solution), the perovskite precursor solution is dripped on the Electron Transport Layer (ETL) prepared in the step (2), and the solution is uniformAfter the perovskite light absorption layer is distributed on an Electron Transport Layer (ETL), starting a spin coater, spin-coating for 60s at the rotating speed of 2000rpm, dropwise adding 80 mu L of ethyl acetate in 15-16 s before the spin coating is finished, then annealing (a heating table is started in advance, the temperature is set to be 130 ℃, after the temperature of the heating table is raised to 130 ℃ and stabilized, the substrate which is spin-coated with the perovskite layer is placed on the heating table for annealing, the temperature of the heating table is kept stable in the annealing process, and the substrate is taken down after 30 min), thus preparing the perovskite light absorption layer on the Electron Transport Layer (ETL).
(4) Preparation of Hole Transport Layer (HTL): 30 μ L of a solution containing a Hole Transport Layer (HTL) material (20 mg of poly [ bis (4-phenyl) (2,4,6-trimethylphenyl) amine ] (PTAA) dissolved in toluene, and 4.0 μ L of tBP and 3.20 μ L of a 1.8mol/L solution of Li-TFSI acetonitrile were added thereto) was dropped on the perovskite light-absorbing layer prepared in step (3) with shaking for 5min, sonicated for 10min, filtered through a 0.22 μ M PTFE membrane), and a spin coater was started to spin coat (rotation speed set at 4000rpm, time set at 25 s) the perovskite light-absorbing layer to prepare a Hole Transport Layer (HTL) thereon.
(5) Preparing a metal back electrode: setting the pressure of the vapor deposition instrument to 1 × 10 -4 Pa, on the hole transport layer prepared in step (4) by thermal evaporation, first
Figure BDA0003399315570000081
At a speed of 10nm, and then evaporating Al in->
Figure BDA0003399315570000082
And evaporating 70nm of Al at the speed of the film deposition rate to finally prepare an Al electrode with the thickness of 80nm, namely forming a metal back electrode on a Hole Transport Layer (HTL) to obtain the perovskite solar cell containing large-size strong coordination organic anion potassium salt.
Comparative example
The perovskite precursor solution containing the monopotassium salt of 4-sulfobenzoic acid and the perovskite light-absorbing layer material used in the preparation of the perovskite light-absorbing layer in example 1 was changed to a perovskite precursor solution containing only the perovskite light-absorbing layer material without monopotassium salt of 4-sulfobenzoic acid (formamidine hydroiodide (248.16 mg), csI (19.73 mg), rbI (6.58 mg), pbI 2 (682.73mg)、PbBr 2 (8.53mg)、PbCl 2 (12.74 mg) and methylamine hydrochloride (35 mg) were dissolved in a mixed solvent of N, N-dimethylformamide (800 μ L) and dimethyl sulfoxide (200 μ L), and shaken for 10min and sonicated for 10min, and the remaining preparation methods were completely the same as those in example 1, and a perovskite solar cell was prepared.
FIG. 1 shows 4-sulfobenzoic acid monopotassium salt molecule and FAPBI 3 A is a schematic diagram of several interaction modes of formamidine hydroiodide, lead iodide and 4-sulfobenzoic acid monopotassium salt in perovskite components (FAI-I-FAI-VI is six different interaction modes between 4-sulfobenzoic acid monopotassium salt molecules and formamidine hydroiodide, pbI 2 -I～PbI 2 VI is respectively 4-sulfobenzoic acid monopotassium salt molecule and PbI 2 Six different modes of action); b is the formation energy of several cases shown in a in figure 1 calculated according to DFT; c is a state density calculation result diagram of a plurality of interaction modes shown in a in figure 1 (perovskites are perovskites, SAMS-PVSK is perovskite containing 4-sulfobenzoic acid monopotassium salt molecules, and 4-SBA is 4-sulfobenzoate anions). As can be seen from FIG. 1, FAPBI 3 The perovskite and the monopotassium 4-sulfobenzoate have strong interaction, and the FAPBI 3 The valence band maximum and conduction band minimum states of the perovskite are unchanged, namely the introduction of the large-size strongly coordinated anionic potassium salt (4-sulfobenzoic acid monopotassium salt molecule) does not change FAPBI 3 Excellent band gap of (2).
Fig. 2 is an X-ray photoelectron spectroscopy (XPS) chart of 4-sulfobenzoic acid monopotassium salt molecules (SAMS), a perovskite solar cell light-absorbing layer (comparative example) prepared in comparative example and not containing 4-sulfobenzoic acid monopotassium salt molecules, and a perovskite solar cell light-absorbing layer (example 1) containing 4-sulfobenzoic acid monopotassium salt molecules in example 1, and it can be seen from fig. 2 that a strong chemical action is provided between the perovskite light-absorbing layer and the original components of perovskite.
FIG. 3 shows a mixture of 4-sulfobenzoic acid monopotassium molecule (SAMS), lead iodide and 4-sulfobenzoic acid monopotassium (PbI) 2 + SAMS), comparative example does not contain 4-Light-absorbing layer of perovskite solar cell containing single potassium sulfobenzoate molecule (comparative example), light-absorbing layer of perovskite containing single potassium 4-sulfobenzoate molecule in example 1 (example 1) 13 C nmr spectrum, as can be seen from fig. 3, it is confirmed that the perovskite solar cell light-absorbing layer containing the 4-sulfobenzoic acid monopotassium salt molecule can be obtained by adding the 4-sulfobenzoic acid monopotassium salt molecule to the perovskite solar cell light-absorbing layer by the method of step (3) in example 1, and the 4-sulfobenzoic acid monopotassium salt molecule has a strong chemical action with the original perovskite component.
Fig. 4 is a time-of-flight secondary ion mass spectrum of a perovskite solar cell not containing a 4-sulfobenzoic acid monopotassium salt molecule in comparative example (comparative example) and a perovskite solar cell containing a 4-sulfobenzoic acid monopotassium salt molecule in example 1 (example 1), wherein a fresh sample refers to a perovskite solar cell which is just prepared and is not irradiated with light. As can be seen from fig. 4, in the fresh sample prepared in comparative example and the fresh sample prepared in example 1, chloride ions (Cl) in the Hole Transport Layer (HTL) were present - ) The content is equivalent; however, after 1320 hours of illumination, cl in the Hole Transport Layer (HTL) of example 1 - The increase is less, which shows that the addition of the 4-sulfobenzoic acid monopotassium salt molecule to the light absorption layer of the perovskite solar cell in example 1 can effectively inhibit the ion migration in the perovskite thin film.
FIG. 5 is a time-resolved microwave conductivity test plot for the perovskite solar cell light-absorbing layer prepared in comparative example and example 1, which may be used to characterize the carrier mobility of the perovskite solar cell light-absorbing layer, and it can be seen from FIG. 5 that the perovskite solar cell light-absorbing layer prepared in comparative example has a carrier mobility of about 45cm 2 V -1 S -1 While the perovskite solar cell prepared in example 1 has a carrier mobility of about 51cm 2 V -1 S -1 It is demonstrated that the mobility of the carrier of the perovskite solar cell light absorption layer modified by the 4-sulfobenzoic acid monopotassium salt molecule according to the method of embodiment 1 of the present invention is significantly increased.
Fig. 6 is a time-resolved photoluminescence (TRPL) spectrum of the perovskite solar cell light absorption layer prepared in the comparative example and example 1 measured under the excitation condition of 468nm, which can be used to characterize the carrier lifetime, and as can be seen from fig. 6, the carrier lifetime of the perovskite solar cell light absorption layer prepared in the comparative example is 1.30 μ s, while the carrier lifetime of the perovskite solar cell light absorption layer prepared in example 1 is 2.06 μ s, which illustrates that the lifetime of the perovskite solar cell light absorption layer prepared in the method of example 1 of the present invention is significantly improved after the perovskite solar cell light absorption layer is modified by the monopotassium salt molecule of 4-sulfobenzoic acid.
FIG. 7 shows perovskite solar cells in comparative example and example 1 at 100mW/cm 2 Under the sunlight simulation light source, forward scanning current density-voltage (J-V) curves measured at a scanning speed of 50mV/S are shown in Table 1, and photovoltaic parameters measured at a scanning speed of 50mV/S are shown in FIG. 7 and Table 1.
TABLE 1 photovoltaic parameters measured at a sweep rate of 50mV/s
Figure BDA0003399315570000101
Fig. 8 is a graph showing the results of the humidity stability test of the unencapsulated perovskite solar cell in comparative example and example 1, which was continuously placed in air at 20-30% relative humidity, and it can be seen from fig. 8 that the unencapsulated perovskite solar cell in example 1 maintained 98% of the initial efficiency after aging for 1320 hours under the relative humidity condition of 20-30%, which is significantly higher than that of the perovskite solar cell in comparative example.
Fig. 9 is a graph showing the results of thermal stability tests performed on the unencapsulated perovskite solar cell in comparative example and example 1, which was continuously placed in a nitrogen atmosphere at 60 ℃, and it can be seen from fig. 9 that the unencapsulated perovskite solar cell in example 1 maintained 99% of the initial efficiency after being aged at 60 ℃ for 1320 hours, which is significantly higher than that of the comparative example.
Similarly, the perovskite solar cell containing the large-size strongly coordinating organic anion potassium salt prepared in example 2 and example 3 was subjected to performance test, and the result is the same as the perovskite solar cell containing the large-size strongly coordinating organic anion potassium salt prepared in example 1 in performance, the service life of the perovskite solar cell is not less than 2.06 μ s, and the perovskite solar cell has a power conversion efficiency of not less than 22.68%; meanwhile, the perovskite solar cell has excellent long-term stability (98% of the initial efficiency can be maintained after 1320h when the perovskite solar cell is placed in an environment with the relative humidity of 20-30%; and 99% of the initial efficiency can be maintained after 1320h when the perovskite solar cell is placed in an environment with the temperature of 60 ℃).
In conclusion, the invention discloses application of potassium salt containing large-size strongly coordinated organic anions in a perovskite solar cell, namely, the potassium salt containing the large-size strongly coordinated organic anions, which contain carboxyl and sulfonic acid groups and can perform strong coordination with uncoordinated lead ions, is used for preparing the perovskite solar cell. Because the sulfonic acid functional group and the carboxyl functional group contained in the large-size strong coordination organic anion potassium salt can be combined with the uncoordinated lead ion Pb 2+ And/or the halogen vacancies are strongly coordinated and interacted, so that the perovskite solar cell is firmly anchored in the crystal boundary of the perovskite solar cell, the crystal boundary ion migration and the crystal boundary defect passivation are synergistically inhibited, the perovskite solar cell is effectively inhibited from being separated, the carrier mobility is obviously increased, the carrier service life of the perovskite thin film is prolonged, and meanwhile, the non-radiative recombination of the carriers at the interface is greatly reduced, so that the power conversion efficiency and the long-term stability of the perovskite solar cell are improved, and an effective method for efficiently stabilizing the perovskite solar cell is provided; the invention also discloses a perovskite solar cell containing the large-size strong coordination organic anion sylvite, wherein the perovskite light absorption layer in the perovskite solar cell contains the large-size strong coordination organic anion sylvite, the service life of the perovskite solar cell is prolonged to 2.06 mu s, and the perovskite solar cell has the highest power conversion efficiency of 22.68%; meanwhile, the perovskite solar cell shows excellent long-term stability (the perovskite solar cell is placed in an environment with the relative humidity of 20-30% and passes through 1After 320h, 98% of the initial efficiency can be maintained; it was placed in a 60 ℃ temperature environment and 99% of the initial efficiency was maintained after 1320 h). Therefore, the perovskite solar cell containing the large-size strongly coordinated organic anion disclosed by the invention has very important significance for promoting the commercialization process of the perovskite solar cell.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.

Claims (8)

1. The application of potassium salt containing large-size strongly-coordinated organic anions in a perovskite solar cell is characterized in that the large-size strongly-coordinated organic anions in the potassium salt containing the large-size strongly-coordinated organic anions contain carboxyl and sulfonic acid groups, and the large-size strongly-coordinated organic anions can generate strong coordination with uncoordinated lead ions;
the potassium salt containing the large-size strong coordination organic anion is 4-sulfobenzoic acid monopotassium salt.
2. The application according to claim 1, characterized in that it is in particular: the potassium salt containing large-size strong coordination organic anions is added into a perovskite light absorption layer of a perovskite solar cell and is used for modifying the perovskite light absorption layer.
3. The perovskite solar cell containing the large-size strong coordination organic anion sylvite is characterized in that a perovskite light absorption layer in the perovskite solar cell contains the large-size strong coordination organic anion sylvite;
the large-size strong coordination organic anion potassium salt is 4-sulfobenzoic acid monopotassium salt.
4. The perovskite solar cell according to claim 3, comprising, from bottom to top, an electrically conductive substrate layer, an electron transport layer, a perovskite light absorbing layer comprising a large-size strongly coordinating organic anion potassium salt, a hole transport layer and a metal back electrode.
5. The perovskite solar cell of claim 4, wherein the conductive substrate layer is ITO conductive glass or FTO conductive glass;
the material of the electron transport layer is any one or more of tin dioxide, titanium dioxide, zinc oxide, barium stannate or cerium dioxide;
the material of the hole transport layer is any one or more of 2,2',7,7' -tetra [ N, N-di (4-methoxyphenyl) amino ] -9,9' -spirobifluorene, poly [ bis (4-phenyl) (2,4,6-trimethylphenyl) amine ], poly (3-hexylthiophene-2,5-diyl), cuprous thiocyanate, cuprous iodide or nickel oxide;
the metal back electrode is made of any one of gold, silver, aluminum or low-temperature carbon.
6. The perovskite solar cell of claim 4, wherein the material of the perovskite light absorption layer further comprises ABX 3 Wherein A is CH 3 NH 3 + 、CH(NH 2 ) 2 + 、Cs + Or Rb + B is Pb 2+ 、Sn 2+ Or Ge 2+ At least one of (1), X is Cl - 、Br - Or I - At least one of (1).
7. A method of manufacturing a perovskite solar cell as claimed in any one of the claims 3 to 6, characterized in that the method of manufacturing comprises the steps of:
(1) Preparing an electron transport layer: dropwise adding a solution containing an electron transport layer material onto a pretreated conductive substrate, spin-coating, annealing, and then performing ultraviolet ozone irradiation or Plasma treatment to form an electron transport layer on the conductive substrate;
(2) Preparing a perovskite light absorption layer: spin-coating a perovskite precursor solution containing a potassium salt of a large-size strong coordination organic anion and a perovskite light absorption layer material on the electron transport layer prepared in the step (1), dropwise adding an anti-solvent, annealing, and preparing a perovskite light absorption layer on the electron transport layer;
(3) Preparing a hole transport layer: dropwise adding a solution containing a hole transport layer material on the perovskite light absorption layer prepared in the step (3), and performing spin coating to prepare a hole transport layer on the perovskite light absorption layer;
(4) Preparing a metal back electrode: and (4) preparing a metal back electrode on the hole transport layer prepared in the step (4).
8. The method of claim 7, wherein the pre-treatment is: sequentially ultrasonically cleaning the conductive substrate by using a detergent, deionized water, acetone and absolute ethyl alcohol, blow-drying the conductive substrate by using nitrogen, carrying out ultraviolet ozone treatment on the conductive substrate, and cooling the conductive substrate;
the concentration of lead ions in the perovskite precursor solution is 0.5-2.5 mol/L, the concentration of large-size strongly-coordinated organic anion sylvite in the perovskite precursor solution is 0.01-5.0 mg/mL, and the solvent in the perovskite precursor solution is one or two of N, N-dimethylformamide or dimethyl sulfoxide;
the spin coating specifically comprises the following steps: the rotating speed is 2000-6000 rpm, and the spin coating time is 20-60 s;
the annealing specifically comprises the following steps: the temperature is 100-200 ℃, and the annealing time is 10-60 min;
the anti-solvent is any one or more of dichloromethane, dichlorobenzene, toluene, ethyl acetate, chloroform, diethyl ether or chlorobenzene.
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