CN117177641A - Method for preparing perovskite precursor solution and perovskite photovoltaic cell - Google Patents
Method for preparing perovskite precursor solution and perovskite photovoltaic cell Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 74
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- 238000002161 passivation Methods 0.000 claims abstract description 37
- 229910001508 alkali metal halide Inorganic materials 0.000 claims abstract description 11
- 150000008045 alkali metal halides Chemical class 0.000 claims abstract description 11
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 72
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- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 238000005303 weighing Methods 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
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- 239000010409 thin film Substances 0.000 claims description 9
- -1 halogen ion Chemical group 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- KLZMUJRJFXYDCW-UHFFFAOYSA-N 2-[6-(diaminomethylideneamino)hexyl]guanidine;hydrochloride Chemical compound Cl.NC(N)=NCCCCCCN=C(N)N KLZMUJRJFXYDCW-UHFFFAOYSA-N 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical class CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical group [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000002892 organic cations Chemical class 0.000 claims description 3
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- DLFDEDJIVYYWTB-UHFFFAOYSA-N dodecyl(dimethyl)azanium;bromide Chemical compound Br.CCCCCCCCCCCCN(C)C DLFDEDJIVYYWTB-UHFFFAOYSA-N 0.000 description 11
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- 238000002425 crystallisation Methods 0.000 description 6
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
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- XIOYECJFQJFYLM-UHFFFAOYSA-N 2-(3,6-dimethoxycarbazol-9-yl)ethylphosphonic acid Chemical compound COC=1C=CC=2N(C3=CC=C(C=C3C=2C=1)OC)CCP(O)(O)=O XIOYECJFQJFYLM-UHFFFAOYSA-N 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- HTMQZWFSTJVJEQ-UHFFFAOYSA-N benzylsulfinylmethylbenzene Chemical compound C=1C=CC=CC=1CS(=O)CC1=CC=CC=C1 HTMQZWFSTJVJEQ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- JAHFQMBRFYOPNR-UHFFFAOYSA-N iodomethanamine Chemical compound NCI JAHFQMBRFYOPNR-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The application provides a method for preparing perovskite precursor solution and a perovskite photovoltaic cell. The method for preparing the perovskite precursor solution comprises the following steps: providing a lead halide composite single crystal; mixing the lead halide composite single crystal, inorganic alkali metal halide and organic ammonium salt according to a certain molar ratio, and dissolving the mixture in a solvent to obtain a perovskite precursor solution, or dissolving the lead halide composite single crystal in the solvent to form a first precursor solution, and preparing an organic ammonium salt/inorganic alkali metal halide solution to form a second precursor solution. Therefore, in the perovskite precursor solution prepared by the method, the coordination effect of lead halide and the passivation material is better, and furthermore, the perovskite film is prepared by using the perovskite precursor solution, so that the obtained perovskite film has better crystal boundary passivation effect and better structural stability.
Description
Technical Field
The application relates to the technical field of solar cells, in particular to a method for preparing perovskite precursor solution and a perovskite photovoltaic cell.
Background
The perovskite photovoltaic cell continuously refreshes the highest efficiency within a short period of tens of years, the highest single-cell battery reaches 25.5%, but the perovskite photovoltaic cell has the defects of poor stability, more defects and the like no matter in an upright structure or an inverted structure, and the perovskite has more passivation means, mostly small molecular additives, but the long-term stability of the prepared perovskite is still not too high. The phase transition of perovskite is one of the main causes of perovskite instability, and its core is lead iodide (PbI 2 ) Degradation under light causes the degraded lead to form new non-radiative recombination centers in the perovskite and inhibits the generation and transport of charge carriers. The prior method is to fill the defects in perovskite or to fill PbI by adding additives 2 Coordination is formed to reduce phase transformation, but in the prior art, the additive is mostly directly added into the perovskite precursor, and in this way, part of the additive is still in a free state and is in contact with PbI 2 The coordination effect of (c) is not complete, resulting in an undesirable passivation effect.
Disclosure of Invention
The present application aims to solve at least one of the technical problems in the related art to some extent. Therefore, an object of the present application is to provide a method for preparing a perovskite precursor solution, wherein the perovskite precursor solution prepared by the method is used for preparing a perovskite film, and the perovskite film has better grain boundary passivation effect and better structural stability than the perovskite film prepared by the general method.
In one aspect of the application, a method of preparing a perovskite precursor solution is provided. According to an embodiment of the present application, a method of preparing a perovskite precursor solution includes the steps of: providing a lead halide composite single crystal; mixing the lead halide composite monocrystal, the inorganic alkali metal halide and the organic ammonium salt according to a certain molar ratio, and dissolving the mixture in a solvent to obtain the perovskite precursor solution, or dissolving the lead halide composite monocrystal in the solvent to form a first precursor solution, and preparing the organic ammonium salt/inorganic alkali metal halide solution to form a second precursor solution. Therefore, in the perovskite precursor solution prepared by the method, the coordination effect of the lead halide and the passivation material is good, the lead halide in a free state is greatly reduced, and furthermore, the perovskite film is prepared by using the perovskite precursor solution, the grain boundary passivation effect of the obtained perovskite film is good, and the structural stability of the perovskite film is better.
According to an embodiment of the application, the solute component in the perovskite precursor solution is ABX 3 Wherein the element A is a metal cation or an organic cation, the element B is a lead ion, and the element X is a halogen ion, preferably ABX 3 Is Cs m FA n PbX 3 Or Cs m MA n PbX 3 Wherein m+n=1, 0.ltoreq.m.ltoreq.1, 0.ltoreq.n.ltoreq.1.
According to an embodiment of the present application, the lead halide composite single crystal includes a lead halide and a passivation material, and the lead halide and the passivation material form a coordination.
According to an embodiment of the present application, in the method for preparing a perovskite precursor solution, the passivation material includes at least one of a quaternary ammonium salt, a transition metal acid salt, a methylimidazole salt, and a hexamethyleneguanidine hydrochloride, and optionally, the passivation material is a quaternary ammonium salt having a structural formula of R 4 N + X - Wherein X is - Is halogen anion, and the structural formula for forming the lead halide composite monocrystal is R 4 NPbX 3 。
According to an embodiment of the present application, in the method of preparing a perovskite precursor solution, the method of preparing a lead halide composite single crystal includes: weighing lead halide and a passivation material according to a certain molar ratio, and dissolving the lead halide and the passivation material in a good solvent to obtain a first solution; placing a proper amount of the first solution into a first container; adding a proper amount of poor solvent into a second container, placing the first container into the second container, and enabling the first solution to be not contacted with the poor solvent; sealing the second container and leaving the first container open in the second container; and placing the first container and the second container for a period of time, volatilizing and mixing the good solvent and/or the poor solvent, so that the good solvent in the first solution is reduced and the solute is separated from the good solvent, and obtaining the lead halide composite single crystal.
According to an embodiment of the present application, in the method of producing a lead halide composite single crystal, the good solvent includes at least one of dichloromethane, chloroform, and methanol.
According to an embodiment of the present application, in the method of producing a lead halide composite single crystal, the poor solvent includes at least one of N, N-dimethylformamide, N-hexane, diethyl ether.
According to an embodiment of the present application, in the first solution, the molar ratio of the lead halide to the passivation material is 1: (0.1 to 1), preferably 1: (0.75-1).
According to an embodiment of the present application, in the method of producing a lead halide composite single crystal, the first container and the second container are placed in a dark and cool environment.
In another aspect of the application, a perovskite photovoltaic cell is provided. According to an embodiment of the application, the perovskite photovoltaic cell comprises a perovskite thin film, a carrier transport layer and an electrode layer, wherein the perovskite thin film is prepared from a perovskite precursor solution prepared by the method. Therefore, the perovskite photovoltaic cell has better structural stability and longer service life.
Additional aspects and advantages of the application will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the application.
Detailed Description
The scheme of the present application will be explained below with reference to examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the present application and should not be construed as limiting the scope of the application. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The application will now be described with reference to specific examples, which are intended to be illustrative only and not limiting in any way.
In one aspect of the application, a method of preparing a perovskite precursor solution is provided. According to an embodiment of the present application, a method of preparing a perovskite precursor solution includes the steps of:
s100: a lead halide composite single crystal is provided.
In some embodiments of the application, the lead halide composite single crystal includes a lead halide and a passivation material, wherein the lead halide and the passivation material form a coordination. According to an embodiment of the application, the passivating material comprises at least one of a quaternary ammonium salt, a transition metal acid salt, a methylimidazole salt, and a hexamethyleneguanidine hydrochloride. In the lead halide composite single crystal, the passivation materials can effectively form coordination with lead halide to obtain the lead halide composite single crystal with stable structure. In some embodiments of the present application, the passivation material is a quaternary ammonium salt, and in some embodiments, the quaternary ammonium salt has the formula R 4 N + X - Wherein X-is a halogen anion, for example, the quaternary ammonium salt can be dodecyl dimethyl ammonium bromide, and the lead halide composite single crystal formed by the method has the structural formula of R 4 NPbX 3 . Thus, the quaternary ammonium salt and the lead halide can prepare the lead halide composite monocrystal with better structural performance, and the finally prepared perovskite film has better structural stability.
According to an embodiment of the present application, the method for preparing the lead halide composite single crystal may be an antisolvent vapor assisted crystallization (AVC), an Inverse Temperature Crystallization (ITC), a temperature reduced crystallization (LTC), or the like. The anti-solvent crystallization method will be described in detail below.
According to an embodiment of the present application, a method for preparing a lead halide composite single crystal using an anti-solvent crystallization method includes:
s110: weighing lead halide and passivation material according to a certain molar ratio, and dissolving the lead halide and passivation material in a good solvent to obtain a first solution.
In some embodiments, the molar ratio of lead halide to passivation material is 1: (0.1-1), such as the molar ratio of 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.65, 1:0.7, 1:0.75, 1:0.8, 1:0.9, 1:1, and the like, the lead halide and the passivation material are weighed according to the proportion, so that the passivation material can be fully coordinated with the lead halide. In some embodiments, the molar ratio of lead halide to passivation material is 1: (0.75-1), the lead halide composite single crystal is prepared by using the lead halide and the passivation material in the proportion range, so that the lead halide composite single crystal can be prepared more efficiently, and the prepared lead halide composite single crystal has better structural stability. If the amount of the lead halide is too large, the lead halide is not completely coordinated, so that the lead halide in the finally prepared perovskite film is not completely coordinated, the uncomplexed lead halide in the perovskite film can be degraded after long-time illumination, the perovskite film is poor in stability, and the degraded lead can form a new non-radiative recombination center in the perovskite and inhibit the generation and transmission of charge carriers, so that the carriers are reduced, and the perovskite photovoltaic cell is severely attenuated.
In some embodiments, the good solvent in the first solution comprises at least one of dichloromethane, chloroform, methanol. The solvent can well dissolve lead halide and passivation materials. The ratio of the solute (i.e., lead halide and passivation material) and the good solvent in the first solution is not particularly limited, so long as the solute is ensured to be completely dissolved in the good solvent.
S120: an appropriate amount of the first solution is placed in a first container.
According to an embodiment of the application, the first container is an open container, such as a container for a sample bottle, beaker, test tube, mass spectrometry bottle, or the like.
S130: and adding an appropriate amount of poor solvent into the second container, placing the first container into the second container, and enabling the first solution not to contact with the poor solvent.
According to an embodiment of the application, the second container is an open container, such as a container for a sample bottle, beaker, test tube, mass spectrometry bottle, or the like. The volume ratio of the first container to the second container is not particularly limited as long as the second container can accommodate the first container and the poor solvent.
In some embodiments, the poor solvent comprises at least one of N, N-dimethylformamide, N-hexane, diethyl ether. The solvent is volatile matter, and the lead halide and the passivation material can not be dissolved in the solvent or are slightly dissolved in the solvent, so that the lead halide and the passivation material in the first solution can well precipitate crystals in the vapor atmosphere of the solvent to form the lead halide composite monocrystal with a better structure. The amount of the poor solvent is not particularly required, and the amount of the poor solvent is ensured to be more than that of the good solvent, so that the good solvent can be fully extracted by the poor solvent, and the good solvent in the first solution is gradually reduced, so that the solute in the first solution is supersaturated to separate out crystals, and the lead halide composite single crystal is prepared.
S140: the second container is sealed and the first container is left open in the second container.
Thus, the first solution in the first container and the poor solvent in the second container can be simultaneously in a sealed environment, and the solution in the first container can be communicated with the poor solution in the second container through gas phase.
S150: and placing the first container and the second container for a period of time, volatilizing and mixing the good solvent and/or the poor solvent in the containers, so that the good solvent in the first solution is reduced and the solute is separated from the good solvent, and obtaining the lead halide composite single crystal. In this process, the poor solvent and the poor solvent volatilize, and the poor solvent gradually dissolves in the first container, and the lead halide composite single crystal gradually precipitates as the poor solvent and the solution in the first container are mixed in the above process due to the low solubility of the lead halide in the poor solvent. In this step, since the growth time of the single crystal is not fixed, it may take 1 hour to 1 day depending on the concentration of the solution preparation, and thus the holding time of the first container and the second container is not fixed, and the holding time period may be selected by those skilled in the art depending on the actual situation, and is not limited herein.
In some embodiments, the first container and the second container are placed in a dark, cool environment. Therefore, degradation of lead halide under illumination can be avoided, so that poor crystallization efficiency and unstable crystal structure are caused.
In some embodiments of the application, X is elemental iodine, i.e., the single crystal formed is a composite single crystal of lead iodide.
According to the embodiment of the application, the method for preparing the lead halide composite single crystal has simple process, does not increase the complexity of the process for preparing the perovskite precursor solution, and has higher yield.
According to an embodiment of the present application, the method for preparing a perovskite precursor solution using the above-mentioned lead halide composite single crystal may include a one-step method and a two-step method, and the one-step method and the two-step method are described in detail below:
in some embodiments of the present application, a method for preparing a perovskite precursor solution by a one-step method using the above-described lead halide composite single crystal includes: s200: the lead halide composite single crystal, inorganic alkali metal halide (such as inorganic alkali metal halide of cesium halide, rubidium halide and the like) and organic ammonium salt (such as iodoformamide FAI or iodomethylamine MAI) are mixed according to a certain molar ratio and dissolved in a solvent to obtain perovskite precursor solution.
In other embodiments of the present application, a method for preparing a perovskite precursor solution by a two-step method using the above-described lead halide composite single crystal includes: s300: and dissolving the lead halide composite monocrystal in the solvent to form a first precursor solution, and preparing an organic ammonium salt/inorganic alkali metal halide solution to form a second precursor solution. The first precursor solution and the second precursor solution together form a perovskite precursor solution, that is, in the two-step method, the perovskite precursor solution includes two parts of the first precursor solution and the second precursor solution. And then when the perovskite film is prepared, the first precursor solution and the second precursor solution are respectively coated on a substrate, namely, the first precursor solution is coated, then the second precursor solution is coated, and the two precursor solutions react after the two precursor solutions are coated, so that the perovskite film is obtained.
According to the embodiment of the application, the choice of the solvent in the prepared perovskite precursor solution is not particularly required, and a person skilled in the art can choose according to actual needs, so long as the lead halide composite single crystal, the inorganic alkali metal halide and the organic ammonium salt can be dissolved. In some embodiments of the present application, the solvent may be at least one of N, N-Dimethylformamide (DMF), dimethylsulfoxide (DMSO), N-methylpyrrolidone (NMP), and Acetonitrile (ACN). The solvents can well dissolve lead halide composite single crystals, inorganic alkali metal halides and organic ammonium salts to obtain uniform and stable perovskite precursor solution.
In some embodiments of the present application, the solute component in the perovskite precursor solution prepared by the above method is ABX 3 Wherein, the element A is metal cation or organic cation, the element B is lead ion, and the element X is halogen ion. In some embodiments, ABX 3 Is Cs m FA n PbX 3 Or Cs m MA n PbX 3 Wherein m+n=1, 0.ltoreq.m.ltoreq.1, 0.ltoreq.n.ltoreq.1; for example, the solute component is CsPbX 3 、FAPbX 3 、Cs 0.5 FA 0.5 PbX 3 、Cs 0.15 FA 0.85 PbX 3 、Cs 0.15 MA 0.85 PbX 3 Etc.
In summary, according to the embodiment of the application, in the perovskite precursor solution prepared by the method, the coordination effect of lead halide and passivation material is better, the lead halide in a free state is greatly reduced, and furthermore, the perovskite film is prepared by using the perovskite precursor solution, so that the obtained perovskite film has better crystal boundary passivation effect and better structural stability. And the method for preparing the lead halide composite single crystal is simpler, and does not complicate the perovskite precursor solution and the preparation process of the perovskite thin film.
In another aspect of the application, a perovskite photovoltaic cell is provided. According to an embodiment of the present application, the perovskite photovoltaic cell includes a perovskite thin film, a carrier transport layer, and an electrode layer, wherein the perovskite thin film is prepared from a perovskite precursor solution prepared by the method described above. Therefore, the perovskite photovoltaic cell has better structural stability and longer service life.
According to the embodiment of the application, the perovskite film is prepared by adopting the perovskite precursor solution, and the method for further preparing the perovskite photovoltaic cell is not particularly required, and a person skilled in the art can select a proper existing conventional method according to actual conditions to prepare the perovskite film.
Specifically, according to some embodiments of the present application, a method for preparing a perovskite thin film using the above perovskite precursor solution, and further preparing a perovskite photovoltaic cell, may include the steps of:
s400: the perovskite precursor solution is coated onto the substrate, and then the antisolvent is added dropwise. Wherein, the antisolvent can be chlorobenzene. Specifically, if the perovskite precursor solution prepared by the one-step method is adopted, the perovskite precursor solution is directly coated on a substrate, and then an anti-solvent is dripped and the perovskite film is obtained through subsequent annealing treatment; if the perovskite precursor solution prepared by the two-step method is adopted, the first precursor solution and the second precursor solution are respectively coated on a substrate, namely, the first precursor solution is coated, then the second precursor solution is coated, the two precursor solutions react after the two precursor solutions are coated, and then an anti-solvent is dripped and the subsequent annealing treatment is carried out, so that the perovskite film can be obtained.
In some embodiments, the perovskite precursor solution may be applied to the substrate using spin coating, in some embodiments at 800rpm, with an acceleration of 200rpm/s for 4 seconds; the rotation speed is 4000rpm, the acceleration is 1000rpm/s, and the duration is 30s; at the reciprocal of 8s, 400. Mu.L of anti-solvent chlorobenzene was added dropwise.
S500: and annealing the substrate to obtain the perovskite thin film.
In some embodiments, the annealing temperature may be 100-150deg.C, such as 100deg.C, 110deg.C, 120deg.C, 130deg.C, 140deg.C, 150deg.C, etc., and the annealing time may be 30min.
S600: and after the annealing is finished, placing the substrate provided with the perovskite film into vacuum evaporation equipment, and depositing an electron transport layer and an evaporation electrode to obtain the perovskite battery.
In some embodiments, the electron transport layer may be C 60 And BCP (2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline). In some embodiments, the electron transport layer comprises 28nm C 60 And an 8nm BCP (2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline) composite electron transport layer.
In some embodiments, the electrode may be a copper electrode, such as a 100nm Cu electrode.
Examples
Example 1
(1) Lead iodide powder and dodecyl dimethyl ammonium bromide powder were mixed in a ratio of 1:1, using dichloromethane to completely dissolve the mixture to prepare a solution, taking 3mL of the solution from the solution, and transferring the solution into a first container with a capacity of 5 mL;
(2) 8mL of n-hexane was added to a second container having a capacity of 20 mL;
(3) Transferring a first container with the volume of 5mL into a second container with the volume of 20mL, fixing the first container by using a corrosion-resistant plastic sheet, sealing the second container, and unsealing the first container so as to form a closed system inside the second container;
(4) Placing the first container and the second container in a shade (room temperature) and standing for 8 hours, taking out the separated single crystal when the solute in the first container is gradually separated out to form a lead iodide composite single crystal, and drying the single crystal at 80 ℃;
(5) Grinding the lead iodide composite monocrystal prepared in the step (4) into powder according to the following steps of 1:0.15: weighing single crystal powder, csI and FAI according to a molar ratio of 0.85, and adding a solvent to completely dissolve the single crystal powder, the CsI and the FAI to prepare a perovskite precursor solution;
(6) And (3) spin-coating the perovskite precursor solution prepared in the step (5) on a substrate by using a spin-coating method, annealing to prepare a perovskite film, and then depositing a carrier transport layer and evaporating an electrode to obtain the perovskite photovoltaic cell.
Example 2
(1) Lead iodide powder and dodecyl dimethyl ammonium bromide powder were mixed in a ratio of 1:1, using dichloromethane to completely dissolve the mixture to prepare a solution, taking 3mL of the solution from the solution, and transferring the solution into a first container with a capacity of 5 mL;
(2) 6mL of diethyl ether was added to a second vessel having a capacity of 20 mL;
(3) Transferring a first container with the volume of 5mL into a second container with the volume of 20mL, fixing the first container by using a corrosion-resistant plastic sheet, sealing the second container, and unsealing the first container so as to form a closed system inside the second container;
(4) Placing the first container and the second container in a shade place for standing for 8 hours, taking out the precipitated single crystal when the solute in the first container is gradually precipitated to form a lead iodide composite single crystal, and drying the single crystal at 80 ℃;
(5) Grinding the lead iodide composite monocrystal prepared in the step (4) into powder according to the following steps of 1:0.15: weighing single crystal powder, csI and FAI according to a molar ratio of 0.85, and adding a solvent to completely dissolve the single crystal powder, the CsI and the FAI to prepare a perovskite precursor solution;
(6) And (3) spin-coating the perovskite precursor solution prepared in the step (5) on a substrate by using a spin-coating method, annealing to prepare a perovskite film, and then depositing a carrier transport layer and evaporating an electrode to obtain the perovskite photovoltaic cell.
Example 3
(1) Lead iodide powder and dodecyl dimethyl ammonium bromide powder were mixed in a ratio of 1:1, using dichloromethane to completely dissolve the mixture to prepare a solution, taking 3mL of the solution from the solution, and transferring the solution into a first container with a capacity of 5 mL;
(2) 6mL of DMF was added to a second container of 20mL capacity;
(3) Transferring a first container with the volume of 5mL into a second container with the volume of 20mL, fixing the first container bottle by using a corrosion-resistant plastic sheet, sealing the second container, and unsealing the first container, so that a closed system is formed inside the second container;
(4) Placing the first container and the second container in a shade place for standing for 8 hours, taking out the precipitated single crystal when the solute in the first container is gradually precipitated to form a lead iodide composite single crystal, and drying the single crystal at 80 ℃;
(5) Grinding the lead iodide composite monocrystal prepared in the step (4) into powder according to the following steps of 1:0.15: weighing single crystal powder, csI and FAI according to a molar ratio of 0.85, and adding a solvent to completely dissolve the single crystal powder, the CsI and the FAI to prepare a perovskite precursor solution;
(6) And (3) spin-coating the perovskite precursor solution prepared in the step (5) on a substrate by using a spin-coating method, annealing to prepare a perovskite film, and then depositing a carrier transport layer and evaporating an electrode to obtain the perovskite photovoltaic cell.
Example 4
(1) Lead iodide powder and dodecyl dimethyl ammonium bromide powder were mixed in a ratio of 1:1, completely dissolving the mixture into a solution by using methanol, taking 3mL of the solution from the solution, and transferring the solution into a first container with a capacity of 5 mL;
(2) 4mL of diethyl ether was added to a second vessel having a capacity of 20 mL;
(3) Transferring a first container with the volume of 5mL into a second container with the volume of 20mL, fixing the first container by using a corrosion-resistant plastic sheet, sealing the second container, and unsealing the first container so as to form a closed system inside the second container;
(4) Placing the first container and the second container in a shade place for standing for 8 hours, taking the storage of diethyl ether and replenishing diethyl ether timely because diethyl ether volatilizes quickly, taking out the separated monocrystal when solute in the first container is gradually separated out to form lead iodide composite monocrystal, and drying at 80 ℃;
(5) Grinding the lead iodide composite monocrystal prepared in the step (4) into powder according to the following steps of 1:0.15: weighing single crystal powder, csI and FAI according to a molar ratio of 0.85, and adding a solvent to completely dissolve the single crystal powder, the CsI and the FAI to prepare a perovskite precursor solution;
(6) And (3) spin-coating the perovskite precursor solution prepared in the step (5) on a substrate by using a spin-coating method, annealing to prepare a perovskite film, and then depositing a carrier transport layer and evaporating an electrode to obtain the perovskite photovoltaic cell.
Example 5
(1) Lead iodide powder and dodecyl dimethyl ammonium bromide powder were mixed in a ratio of 1: a molar ratio of 0.75 was prepared, and the mixture was completely dissolved in methanol to prepare a solution, from which 3mL of the solution was taken and transferred to a first container having a capacity of 5 mL;
(2) 4mL of diethyl ether was added to a second vessel having a capacity of 20 mL;
(3) Transferring a first container with the volume of 5mL into a second container with the volume of 20mL, fixing the first container by using a corrosion-resistant plastic sheet, sealing the second container, and unsealing the first container so as to form a closed system inside the second container;
(4) Placing the first container and the second container in a shade place for standing for 8 hours, taking the storage of diethyl ether and replenishing diethyl ether timely because diethyl ether volatilizes quickly, taking out the separated monocrystal when solute in the first container is gradually separated out to form lead iodide composite monocrystal, and drying at 80 ℃;
(5) Grinding the lead iodide composite monocrystal prepared in the step (4) into powder according to the following steps of 1:0.15: weighing single crystal powder, csI and FAI according to a molar ratio of 0.85, and adding a solvent to completely dissolve the single crystal powder, the CsI and the FAI to prepare a perovskite precursor solution;
(6) And (3) spin-coating the perovskite precursor solution prepared in the step (5) on a substrate by using a spin-coating method, annealing to prepare a perovskite film, and then depositing a carrier transport layer and evaporating an electrode to obtain the perovskite photovoltaic cell.
Example 6
(1) Lead iodide powder and dodecyl dimethyl ammonium bromide powder were mixed in a ratio of 1: a molar ratio of 0.5 was prepared, and the mixture was completely dissolved in methanol to prepare a solution, from which 3mL of the solution was taken and transferred to a first container having a capacity of 5 mL;
(2) 4mL of diethyl ether was added to a second vessel having a capacity of 20 mL;
(3) Transferring a first container with the volume of 5mL into a second container with the volume of 20mL, fixing the first container by using a corrosion-resistant plastic sheet, sealing the second container, and unsealing the first container so as to form a closed system inside the second container;
(4) Placing the first container and the second container in a shade place for standing for 8 hours, taking the storage of diethyl ether and replenishing diethyl ether timely because diethyl ether volatilizes quickly, taking out the separated monocrystal when solute in the first container is gradually separated out to form lead iodide composite monocrystal, and drying at 80 ℃;
(5) Grinding the lead iodide composite monocrystal prepared in the step (4) into powder according to the following steps of 1:0.15: weighing single crystal powder, csI and FAI according to a molar ratio of 0.85, and adding a solvent to completely dissolve the single crystal powder, the CsI and the FAI to prepare a perovskite precursor solution;
(6) And (3) spin-coating the perovskite precursor solution prepared in the step (5) on a substrate by using a spin-coating method, annealing to prepare a perovskite film, and then depositing a carrier transport layer and evaporating an electrode to obtain the perovskite photovoltaic cell.
Example 7
(1) Lead iodide powder and dodecyl dimethyl ammonium bromide powder were mixed in a ratio of 1: a molar ratio of 0.5 was prepared, and the mixture was completely dissolved in methanol to prepare a solution, from which 3mL of the solution was taken and transferred to a first container having a capacity of 5 mL;
(2) 4mL of diethyl ether was added to a second vessel having a capacity of 20 mL;
(3) Transferring a first container with the volume of 5mL into a second container with the volume of 20mL, fixing the first container by using a corrosion-resistant plastic sheet, sealing the second container, and unsealing the first container so as to form a closed system inside the second container;
(4) Placing the first container and the second container in a 50 ℃ oven to accelerate the reaction, taking the stock of diethyl ether and replenishing diethyl ether timely because diethyl ether volatilizes faster, taking out the separated monocrystal when solute in the first container is gradually separated out to form lead iodide composite monocrystal, and drying at 80 ℃;
(5) Grinding the lead iodide composite monocrystal prepared in the step (4) into powder according to the following steps of 1:0.15: weighing single crystal powder, csI and FAI according to a molar ratio of 0.85, and adding a solvent to completely dissolve the single crystal powder, the CsI and the FAI to prepare a perovskite precursor solution;
(6) And (3) spin-coating the perovskite precursor solution prepared in the step (5) on a substrate by using a spin-coating method, annealing to prepare a perovskite film, and then depositing a carrier transport layer and evaporating an electrode to obtain the perovskite photovoltaic cell.
Example 8
(1) Lead iodide powder and dodecyl dimethyl ammonium bromide powder were mixed according to a ratio of 1: a molar ratio of 0.5 was prepared, and the mixture was completely dissolved in methanol to prepare a solution, from which 3mL of the solution was taken and transferred to a first container having a capacity of 5 mL;
(2) 8mL of diethyl ether was added to a second vessel having a capacity of 20 mL;
(3) Transferring a first container with the volume of 5mL into a second container with the volume of 20mL, fixing the first container by using a corrosion-resistant plastic sheet, sealing the second container, and unsealing the first container so as to form a closed system inside the second container;
(4) Placing the first container and the second container in an oven at 80 ℃ to accelerate the reaction, taking the stock of diethyl ether and replenishing diethyl ether timely because diethyl ether volatilizes faster, taking out the separated monocrystal when solute in the first container is gradually separated out to form lead iodide composite monocrystal, and drying at 80 ℃;
(5) Grinding the lead iodide composite monocrystal prepared in the step (4) into powder according to the following steps of 1:0.15: weighing single crystal powder, csI and FAI according to a molar ratio of 0.85, and adding a solvent to completely dissolve the single crystal powder, the CsI and the FAI to prepare a perovskite precursor solution;
(6) And (3) spin-coating the perovskite precursor solution prepared in the step (5) on a substrate by using a spin-coating method, annealing to prepare a perovskite film, and then depositing a carrier transport layer and evaporating an electrode to obtain the perovskite photovoltaic cell.
Example 9
This example differs from example 4 in that the molar ratio of lead iodide to dodecyldimethylammonium bromide is 1:0.1, the other conditions being the same.
Example 10
This example differs from example 4 in that the molar ratio of lead iodide to dodecyldimethylammonium bromide is 1:1.2, the other conditions being the same.
Example 11
This embodiment differs from embodiment 4 in that, according to 1:0.5: monocrystalline powder, csI and FAI were weighed in a molar ratio of 0.5, with the same other conditions.
Comparative example 1
(1) According to 1:0.15: weighing lead iodide, csI and FAI according to a molar ratio of 0.85, and adding a solvent to completely dissolve the lead iodide, the CsI and the FAI to prepare a perovskite precursor solution;
(2) Adding MeO-2PACz ([ 2- (3, 6-dimethoxy-9H-carbazole-9-yl) ethyl ] phosphonic acid) additive to the perovskite precursor solution prepared in the step (1), wherein the concentration of the MeO-2PACz is 0.05mg/mL;
(3) And (3) spin-coating the perovskite precursor solution prepared in the step (2) on a substrate by using a spin-coating method, annealing to prepare a perovskite film, and then depositing a carrier transport layer and evaporating an electrode to obtain the perovskite photovoltaic cell.
Comparative example 2
(1) According to 1:0.15: weighing lead iodide, csI and FAI according to a molar ratio of 0.85, and adding a solvent to completely dissolve the lead iodide, the CsI and the FAI to prepare a perovskite precursor solution;
(2) Adding a DBSO (dibenzyl sulfoxide) additive to the perovskite precursor solution prepared in the step (1), wherein the concentration of DBSO is 0.15mg/mL;
(3) And (3) spin-coating the perovskite precursor solution prepared in the step (2) on a substrate by using a spin-coating method, annealing to prepare a perovskite film, and then depositing a carrier transport layer and evaporating an electrode to obtain the perovskite photovoltaic cell.
Comparative example 3
(1) According to 1:0.15: weighing lead iodide, csI and FAI according to a molar ratio of 0.85, and adding a solvent to completely dissolve the lead iodide, the CsI and the FAI to prepare a perovskite precursor solution;
(2) And (3) spin-coating the perovskite precursor solution prepared in the step (1) on a substrate by using a spin-coating method, annealing to prepare a perovskite film, and then depositing a carrier transport layer and evaporating an electrode to obtain the perovskite photovoltaic cell. Wherein, the vapor deposited electron transport layerIs C 60 BCP electron transport layer and preparing a layer of Al after BCP using ALD (atomic layer deposition) process 2 O 3 Then, cu electrodes were vapor deposited.
Comparative example 4
(1) According to 1:0.15: weighing lead iodide, csI and FAI according to a molar ratio of 0.85, and adding a solvent to completely dissolve the lead iodide, the CsI and the FAI to prepare a perovskite precursor solution;
(2) And (3) spin-coating the perovskite precursor solution prepared in the step (1) on a substrate by using a spin-coating method, annealing to prepare a perovskite film, and then depositing a carrier transport layer and evaporating an electrode to obtain the perovskite photovoltaic cell.
The perovskite photovoltaic cells prepared in examples 1 to 11 and comparative examples 1 to 4 were subjected to performance testing, and the test data obtained are shown in Table 1:
TABLE 1
As can be seen from the test results, the method can well slow down the attenuation of the perovskite photovoltaic cell by adopting the lead iodide composite single crystal, and the attenuation of the perovskite photovoltaic cell is still serious in comparative examples 1 and 2 despite the addition of passivation materials DBSO and MeO-2 PACz.
Examples 1-3 respectively adopted different poor solvents to prepare lead iodide composite single crystals, and test data in table 1 show that compared with comparative examples 1-4, perovskite photovoltaic cells prepared in examples 1-3 are higher in efficiency and lower in attenuation rate, and the perovskite photovoltaic cells prepared by the technical scheme of the application are relatively good in structural stability and relatively good in performance.
As can be seen from the test data in table 1, the attenuation rate of the perovskite photovoltaic cell prepared by using methanol as the good solvent in example 4 is slightly increased compared with the perovskite photovoltaic cell prepared by using dichloromethane as the good solvent in example 2. This is because a single crystal prepared using methanol is liable to generate finer dendrites during growth, has relatively poor crystallization properties, has a certain structural defect, and causes relatively poor coordination effects of lead iodide and a passivation material in the crystal. However, the perovskite photovoltaic cell prepared in example 4 still had a significantly lower attenuation rate than the perovskite photovoltaic cells prepared in comparative examples 1 to 4.
In examples 4 to 6 and example 9, the molar ratio of the lead iodide to the quaternary ammonium salt in example 4 was sequentially reduced compared to 1:1, and the molar ratio of the quaternary ammonium salt in examples 5, 6 and 9 was sequentially reduced, as can be seen from the test data in table 1, the attenuation rate of the prepared perovskite photovoltaic cell was gradually increased as the amount of the quaternary ammonium salt was reduced, which means that when the amount of the quaternary ammonium salt was reduced, the lead iodide composite single crystal produced was less than 1:1 relative to the molar ratio of the lead iodide to the quaternary ammonium salt in example 4, and part of the lead iodide still had a free state, resulting in incomplete coordination of the lead iodide, which in turn resulted in lower initial efficiency of the prepared perovskite photovoltaic cell, and the attenuation rate was still higher.
In example 10, the molar ratio of the quaternary ammonium salt in example 10 was increased compared with the molar ratio of the lead iodide to the quaternary ammonium salt in example 4, which was 1:1, and it can be seen from the test data in table 1 that the attenuation rate of the perovskite photovoltaic cell prepared in example 10 was significantly increased compared with that in example 4, which means that when the content of the quaternary ammonium salt is higher than that of the lead iodide, the perovskite lattice was distorted due to redundancy caused by the excessively high content of the quaternary ammonium salt, new recombination centers were formed, and the current carrier circulation was blocked, thereby the efficiency was attenuated, and the perovskite photovoltaic cell was more easily degraded.
From the test results of examples 4 to 6 and examples 9 to 10, it was found that the coordination effect between lead iodide and quaternary ammonium salt was optimal and the decay rate of perovskite battery was lowest when the molar ratio of lead iodide and quaternary ammonium salt was 1:1.
Examples 7 to 8, which are increased in heating environment during single crystal precipitation compared with example 6, have a higher heating temperature in example 8 than in example 7. From the test data in table 1, it can be seen that the attenuation rate of the perovskite photovoltaic cell prepared was increased after increasing the heating environment, and the higher the temperature, the higher the attenuation rate was relatively. Under the condition of heating, twin crystals or polycrystal are easy to form in the single crystal, so that the defect density in the crystal is increased, the coordination effect of lead iodide and quaternary ammonium salt in the crystal is relatively slightly poor, and the attenuation of the finally prepared perovskite photovoltaic cell is increased.
In example 11, a different lead iodide single crystal was used in example 11 than in example 4: csI: the perovskite precursor solution is prepared according to the ratio of FAI, and the performances of the obtained perovskite photovoltaic cell are basically consistent with those of the embodiment 4, so that the method for passivating the perovskite by utilizing single crystals can be suitable for different types of perovskite.
In summary, the perovskite precursor solution is prepared by adopting the technical scheme of the application, and the perovskite photovoltaic cell is further prepared, so that the structural stability of the obtained perovskite photovoltaic cell is higher, and the attenuation is slower. And the better good solvent and crystallization environment are adopted, and the better quaternary ammonium salt dosage can lead the coordination effect of lead iodide to reach better level, so that the structure stability of the prepared perovskite photovoltaic cell is better and the comprehensive performance is better.
The terms "first," "second," and the like herein are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present application, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present application have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the application, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the application.
Claims (10)
1. A method of preparing a perovskite precursor solution, comprising the steps of:
providing a lead halide composite single crystal;
mixing the lead halide composite monocrystal, inorganic alkali metal halide and organic ammonium salt according to a certain molar ratio, and dissolving in a solvent to obtain the perovskite precursor solution, or,
and dissolving the lead halide composite monocrystal in the solvent to form a first precursor solution, and preparing an organic ammonium salt/inorganic alkali metal halide solution to form a second precursor solution.
2. The method of claim 1, wherein the solute component in the perovskite precursor solution is ABX 3 Wherein, the element A is metal cation or organic cation, the element B is lead ion, the element X is halogen ion,
preferably, ABX 3 Is Cs m FA n PbX 3 Or Cs m MA n PbX 3 Wherein m+n=1, 0.ltoreq.m.ltoreq.1, 0.ltoreq.n.ltoreq.1.
3. The method of claim 1, wherein the lead halide composite single crystal comprises a lead halide and a passivating material, and the lead halide and the passivating material form a coordination.
4. The method of claim 3, wherein the passivating material comprises at least one of a quaternary ammonium salt, a transition metal acid salt, a methylimidazole salt, and a hexamethyleneguanidine hydrochloride,
optionally, the passivation material is a quaternary ammonium salt, and the structural formula of the quaternary ammonium salt is R 4 N + X - Wherein X is - Is halogen anion, and the structural formula for forming the lead halide composite monocrystal is R 4 NPbX 3 。
5. The method according to claim 3, wherein the method for producing the lead halide composite single crystal comprises:
weighing lead halide and a passivation material according to a certain molar ratio, and dissolving the lead halide and the passivation material in a good solvent to obtain a first solution;
placing a proper amount of the first solution into a first container;
adding a proper amount of poor solvent into a second container, placing the first container into the second container, and enabling the first solution to be not contacted with the poor solvent;
sealing the second container and leaving the first container open in the second container;
and placing the first container and the second container for a period of time, volatilizing and mixing the good solvent and/or the poor solvent, so that the good solvent in the first solution is reduced and the solute is separated from the good solvent, and obtaining the lead halide composite single crystal.
6. The method of claim 5, wherein the good solvent comprises at least one of methylene chloride, chloroform, and methanol.
7. The method of claim 5, wherein the poor solvent comprises at least one of N, N-dimethylformamide, N-hexane, diethyl ether.
8. The method of claim 5, wherein the molar ratio of lead halide to passivation material in the first solution is 1: (0.1 to 1), preferably 1: (0.75-1).
9. The method of claim 5, wherein the first container and the second container are placed in a dark cool environment.
10. A perovskite photovoltaic cell, comprising a perovskite thin film, a carrier transport layer and an electrode layer, wherein the perovskite thin film is prepared from a perovskite precursor solution prepared by the method of any one of claims 1 to 9.
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