阅读说明：本技术 钙钛矿材料粉体的制备方法 (Preparation method of perovskite material powder ) 是由 孙盟杰 郑毅帆 史亦沣 张国栋 邵宇川 于 2021-09-10 设计创作，主要内容包括：一种钙钛矿材料粉体的制备方法,该方法主要步骤为：取组分1与组分2材料进行混合,溶解于良溶剂A,充分搅拌后过滤,得到混合前驱溶液；在混合前驱溶液中加入反溶剂B,快速搅拌至产生钙钛矿微晶沉淀；最后将沉淀清洗,真空干燥即得钙钛矿材料粉体。本发明所述的的制备方法可以使用低纯度原材料合成纯度高、无杂相的钙钛矿材料粉体,用于多种高效薄膜器件制备；并且工艺流程简单快速,无需高温加热,便于高通量产业化合成。(A preparation method of perovskite material powder comprises the following main steps: mixing the component 1 and the component 2, dissolving in a good solvent A, fully stirring, and filtering to obtain a mixed precursor solution; adding an anti-solvent B into the mixed precursor solution, and quickly stirring until perovskite microcrystal precipitation is generated; and finally, cleaning the precipitate, and drying in vacuum to obtain the perovskite material powder. The preparation method can use low-purity raw materials to synthesize perovskite material powder with high purity and no impurity phase, and is used for preparing various high-efficiency thin-film devices; and the process flow is simple and quick, high-temperature heating is not needed, and the high-flux industrial synthesis is facilitated.)

1. The preparation method of the perovskite material powder is characterized by comprising the following steps:

1) dissolving the materials of the component 1 and the component 2 in a good solvent A according to a molar ratio of 1: 1-1: 1.5, stirring until the materials are completely dissolved, and filtering to obtain a mixed precursor solution; wherein, the component 1 is organic amine hydrohalide or alkali metal halide, the component 2 is metal halide, and the good solvent A is aprotic polar solvent; the molar concentration ranges of the component 1 and the component 2 in the good solvent A are 0.5-2.5 mmol/ml;

2) adding an anti-solvent B into the mixed precursor solution, and quickly stirring to generate perovskite microcrystal precipitation;

3) and cleaning the obtained perovskite microcrystal precipitate by using the anti-solvent B, filtering, and drying in vacuum to obtain perovskite material powder.

The perovskite powder consists ofThe component 1 and the component 2 are synthesized, and the chemical formula of the perovskite powder is CMX₃Wherein C is CH₃NH₃ ⁺/MA⁺、NH₂CHNH₂ ⁺/FA⁺、CH₂CH₂CH₂CH₂NH₃ ⁺/BA⁺、C₆H₅CH₂CH₂NH₃ ⁺/PEA⁺、Cs⁺、Rb⁺、Na⁺、K⁺One or two or three of the components are mixed; m is Pb²⁺、Sn²⁺、Zn²⁺、Ba²⁺、Sr²⁺And Ca²⁺One or two of them, or Ag exists at the same time⁺And Bi³⁺(ii) a X is I^-、Br^-、Cl^-One or two of them.

2. The method for preparing perovskite material powder according to claim 1, wherein the component 1 organic amine hydrohalide or alkali metal halide comprises CH₃NH₃X、NH₂CHNH₂X, n-butylamine hydroiodide (CH)₂CH₂CH₂CH₂NH₃I, BAI), phenethylamine hydroiodide (C)₆H₅CH₂CH₂NH₃I, PEAI), CsX, RbX, NaX and KX, wherein X is I^-、Br^-、Cl^-One or two of them.

3. The method for preparing perovskite material powder according to claim 1, wherein the component 2 metal halide is PbX₂、SnX₂、ZnX₂、BaX₂、SrX₂And CaX₂One or two of them, or AgX and BiX exist simultaneously₃。

4. The method for preparing perovskite material powder according to claim 1, wherein the good solvent A and the aprotic polar solvent comprise acetonitrile, diethanol methyl ether, dipropanol methyl ether, dibutyl alcohol methyl ether, ethanolamine, N-dimethylformamide, dimethyl sulfoxide, gamma-butyrolactone or N-methylpyrrolidone.

5. The method for preparing perovskite material powder according to claim 1, wherein the anti-solvent B is a component that does not dissolve any perovskite and is miscible with the good solvent A in any proportion, and comprises diethyl ether, toluene, chlorobenzene, trichloromethane, cyclohexane or ethyl acetate.

6. The method for producing a perovskite material powder as claimed in claim 1, wherein the volume of the added anti-solvent B is 0.5 to 3 times that of the mixed precursor solution.

7. The method for preparing a perovskite material powder as claimed in claim 1, wherein the rapid stirring time is 0.5 to 5 minutes.

Technical Field

The invention belongs to the technical field of material preparation, and particularly relates to a preparation method of perovskite material powder.

Background

Perovskite materials have the characteristics of flexible components, high absorption coefficient, variable band gap, high carrier mobility, long diffusion distance and the like, and are widely applied to the fields of solar cells, photodetectors, light emitting diodes and the like. Currently, the efficiency of Perovskite Solar Cells (PSC) has reached 25%, which exceeds that of conventional polycrystalline silicon solar cells.

In the perovskite solar cell preparation process, impurities substituted by raw materials exist in a perovskite precursor solution, the efficiency of a device is seriously influenced, and the cost for independently purifying the raw materials is high, so that the commercial application of the perovskite device is limited. Meanwhile, the components of the perovskite precursor solution are unstable due to the stoichiometric deviation generated in the preparation process of the perovskite precursor solution, the crystallization condition and the surface morphology of the perovskite film are influenced, the repeatability of the perovskite device is poor, and the large-scale manufacturing of the perovskite device is influenced.

In order to further improve the performance of the perovskite solar cell, reduce the cost of raw materials and improve the reproducibility and yield of devices, researches indicate that the perovskite precursor solution can be prepared by using pre-synthesized perovskite material powder, impurities can be removed from the purified perovskite material powder, and the problems of impurities and stoichiometric deviation described in the previous paragraph can be avoided by fixing components.

At present, the main synthesis methods of perovskite powder comprise a mechanical ball milling method and a wet chemical method, the mechanical ball milling method can realize mass synthesis of materials, but the removal of impurities in raw materials is difficult to solve, and the synthesized powder has poor uniformity; the existing chemical wet method comprises single crystal synthesis and powder synthesis, and the schemes have processes which require long-time heating or stirring and are difficult to adapt to rapid large-scale industrial production. Therefore, a method which can use low-cost and low-purity raw materials, is simple to operate, has a short production flow, is convenient for synthesizing high-purity perovskite material powder on a large scale is sought, and has very important significance for promoting the application of perovskite materials in industrialization.

Disclosure of Invention

The invention aims to provide a preparation method of perovskite material powder, which can be used for synthesizing high-purity perovskite material powder simply, quickly and massively by using low-cost low-purity raw materials.

In order to solve the problems, the technical scheme of the invention is as follows:

the preparation method of the perovskite material powder is characterized by comprising the following steps:

1) dissolving the component 1 and the component 2 materials in a good solvent A according to a molar ratio of 1: 1-1: 1.5, stirring until the components are completely dissolved, and filtering to obtain a mixed precursor solution. Wherein, the component 1 is organic amine hydrohalide or alkali metal halide, the component 2 is metal halide, and the good solvent A is aprotic polar solvent;

2) adding an anti-solvent B into the mixed precursor solution, and quickly stirring to generate perovskite microcrystal precipitation;

3) and cleaning, filtering and vacuum drying the obtained perovskite microcrystal precipitate by using the anti-solvent B to obtain perovskite material powder.

The chemical formula of the perovskite powder in the technical scheme of the invention is CMX₃Wherein C is CH₃NH₃ ⁺/MA⁺、NH₂CHNH₂ ⁺/FA⁺、CH₂CH₂CH₂CH₂NH₃ ⁺/BA⁺、C₆H₅CH₂CH₂NH₃ ⁺/PEA⁺、Cs⁺、Rb⁺、Na⁺、K⁺One or two or three of the components are mixed; m is Pb²⁺、Sn²⁺、Zn²⁺、Ba²⁺、Sr²⁺And Ca²⁺One or two of them, or Ag exists at the same time⁺And Bi³⁺(ii) a X is I^-、Br^-、Cl^-One or two of them.

Preferably, the component 1 organic amine hydrohalide or alkali metal halide described in step (1) comprises CH₃NH₃X、NH₂CHNH₂X, n-butylamine hydroiodide (CH)₂CH₂CH₂CH₂NH₃I, BAI), phenethylamine hydroiodide (C)₆H₅CH₂CH₂NH₃I, PEAI), CsX, RbX, NaX, KX. Wherein X is I^-、Br^-、Cl^-One or two of them.

Preferably, the component 2 metal halide of step (2) is PbX₂、SnX₂、ZnX₂、BaX₂、SrX₂And CaX₂One or two of them, or AgX and BiX exist simultaneously₃。

Preferably, the good solvent A in step (1) is an aprotic polar solvent, including but not limited to acetonitrile, diethanol methyl ether, dipropanol methyl ether, dibutyl methyl ether, ethanolamine, N-dimethylformamide, dimethyl sulfoxide, gamma-butyrolactone, and N-methylpyrrolidone.

Preferably, the molar concentration of the component 1 and the component 2 in the good solvent A in the step (1) is in the range of 0.5-2.5M.

Preferably, the antisolvent B in step (2) is a solvent that does not dissolve any perovskite component and is miscible with the good solvent a in any ratio, including but not limited to diethyl ether, toluene, chlorobenzene, chloroform, cyclohexane, ethyl acetate.

Preferably, the volume of the added antisolvent B in the step (2) is 0.5 to 3 times of the volume of the mixed precursor solution obtained in the step (1).

Preferably, the rapid stirring time in step (2) is 0.5 to 5 minutes.

Preferably, the cleaning solution used in step (3) is an antisolvent B, and the antisolvent B discarded after cleaning can be recovered and recycled by distillation and purification.

Preferably, the chemical formula of the perovskite powder is ABX₃Wherein A is CH₃NH₃ ⁺/MA⁺、NH₂CHNH₂ ⁺/FA⁺、CH₂CH₂CH₂CH₂NH₃ ⁺/BA⁺、C₆H₅CH₂CH₂NH₃ ⁺/PEA⁺、Cs⁺、Rb⁺、Na⁺、K⁺One or two or three of the components are mixed; b is Pb²⁺、Sn²⁺、Zn²⁺、Ba²⁺、Sr²⁺And Ca²⁺One or two of them, or Ag exists at the same time⁺And Bi³⁺(ii) a X is I^-、Br^-、Cl^-One or two of them.

Compared with the prior art, the invention has the advantages that:

1. the perovskite powder preparation method can remove impurities in raw materials, so that the preparation of high-purity perovskite powder from low-purity raw materials is realized, and the raw material cost is greatly reduced;

2. the perovskite powder preparation method has simple and rapid flow, does not need a long-time reaction process, and is convenient for large-scale industrial production;

3. the perovskite powder preparation method disclosed by the invention has the advantages that the used equipment is simple, only test tubes, beakers and stirring equipment are needed, and the equipment cost is extremely low;

4. the preparation method of the perovskite powder is suitable for perovskite powder with various components and has wide applicability.

Drawings

FIG. 1 is a flow chart of a perovskite material powder preparation method of the present invention;

FIG. 2 shows MAPbI prepared in example 1 of the present invention₃Powder (a) photograph and (b) XRD pattern;

FIG. 3 shows MAPbI prepared by example 1 of the present invention₃The perovskite solar cell prepared from powder (column a in the figure) is compared with the perovskite solar cell prepared directly from high-purity raw material (column B in the figure) and low-purity raw material (column C in the figure) using conventional methods.

FIG. 4 shows FAPBI obtained in embodiment 2 of the present invention₃Powder (a) photograph and (b) XRD pattern;

FIG. 5 is a diagram of FAPBI manufactured by the method of embodiment 2 of the present invention₃Perovskite solar cells prepared from powder (column A in the figure) and prepared from high-purity raw materials (column B in the figure) and low-purity raw materials (column B in the figure) by directly using conventional methodColumn C) performance comparison plots for the perovskite solar cells prepared.

FIG. 6 shows MAPbBr prepared in example 5 of the present invention₃Powder (a) photograph and (b) XRD pattern;

Detailed Description

The embodiments of the present invention are described below by way of examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure of the present specification.

FIG. 1 is a flow chart of the preparation method of the present invention

Example 1:

1.5mmol MAI (methylamine hydroiodide, CH) of low-purity raw material₃NH₃I, purity 98%) and 1.5mmol PbI₂(lead iodide, purity 98%) was dissolved in 1ml of ethylene glycol monomethyl ether solvent, and stirring was continued for 1 hour to obtain a mixed solution, which was then filtered and transferred to a small beaker. 2ml of diethyl ether is injected into the beaker, and after 30 seconds of stirring, the black perovskite microcrystal precipitate MAPbI is separated out at the bottom of the beaker₃. Precipitating the perovskite microcrystal precipitate MAPbI obtained by precipitation₃Washing with diethyl ether for 3 times, and vacuum drying at normal temperature to remove residual diethyl ether to obtain the perovskite material powder MAPbI of the embodiment₃The calculated yield was 93%.

The perovskite material powder MAPbI prepared by the embodiment₃The photograph and XRD diffraction pattern are shown in FIG. 2. The XRD pattern shows that the perovskite material powder is of a single crystal form and has no impurity phase. The perovskite powder MAPbI prepared by the example₃A comparison graph of the performance of the prepared perovskite solar cell with that of a perovskite solar cell prepared directly using a conventional method from a low-purity raw material and a high-purity raw material is shown in fig. 3. As can be seen from fig. 3, the low purity raw material severely affected the device efficiency, whereas MAPbI prepared from the low purity raw material purification using this example₃And preparing the perovskite solar cell device after the powder is prepared, wherein the average performance and the repeatability of the device exceed those of the device prepared by high-purity raw materials.

Example 2:

1.5mmol of FAI (formamidine hydroiodide,NH₂CHNH₂i, purity 98%) and 1.5mmol PbI₂(lead iodide, purity 98%) was dissolved in 1ml of ethylene glycol monomethyl ether solvent, and stirring was continued for 1 hour to obtain a mixed solution, which was then filtered and transferred to a small beaker. 2ml of diethyl ether is injected into the beaker, stirred for 30 seconds, and the yellow perovskite microcrystal precipitate FAPbI is separated out at the bottom of the beaker₃. Precipitating the perovskite microcrystal precipitate FAPbI obtained by precipitation₃Washing with diethyl ether for 3 times, and vacuum drying at normal temperature to remove residual diethyl ether to obtain the perovskite material powder FAPBI of the embodiment₃(delta phase), calculated yield 90%.

The perovskite material powder FAPbI prepared by the embodiment₃The XRD diffraction peak positions of the photographs are shown in FIG. 4. The XRD pattern shows that the perovskite material powder is a single crystal form delta phase and has no impurity phase. The perovskite material powder FAPBI prepared by the embodiment₃A comparison graph of the performance of the prepared perovskite solar cell with that of a perovskite solar cell prepared directly using a conventional method from a low-purity raw material, a high-purity raw material is shown in fig. 5. As can be seen in fig. 5, the low purity raw material severely affects the device efficiency, whereas FAPbI is prepared from the low purity raw material purification using this example₃And preparing the perovskite solar cell device after the powder is prepared, wherein the average performance and the repeatability of the device exceed those of the device prepared by high-purity raw materials.

Example 3:

1.5mmol MAI (methylamine hydroiodide, CH) of low-purity raw material₃NH₃I, purity 98%) and 1.5mmol PbI₂(lead iodide, purity 98%) was dissolved in 1ml of γ -butyrolactone solvent, and stirring was continued for 1h to give a mixed solution, which was then filtered and transferred to a small beaker. 2ml of diethyl ether is injected into the beaker, and after 30 seconds of stirring, the black perovskite microcrystal precipitate MAPbI is separated out at the bottom of the beaker₃. Precipitating the perovskite microcrystal precipitate MAPbI obtained by precipitation₃Washing with diethyl ether for 3 times, and vacuum drying at normal temperature to remove residual diethyl ether to obtain the perovskite material powder MAPbI of the embodiment₃The calculated yield was 90%.

Example 4:

1.6mmol FAI (formamidine hydroiodide, NH) of the low-purity starting material₂CHNH₂I, purity 98%) and 1.5mmol PbI₂(lead iodide, purity 98%) was dissolved in 1ml of γ -butyrolactone solvent, and stirring was continued for 1h to give a mixed solution, which was then filtered and transferred to a small beaker. 2ml of diethyl ether is injected into the beaker, stirred for 30 seconds, and the yellow perovskite microcrystal precipitate FAPbI is separated out at the bottom of the beaker₃. Precipitating the perovskite microcrystal precipitate FAPbI obtained by precipitation₃Washing with diethyl ether for 3 times, and vacuum drying at normal temperature to remove residual diethyl ether to obtain the perovskite material powder FAPBI of the embodiment₃The calculated yield was 92%.

Example 5:

1mmol of MABr (methylamine hydrobromide, CH) as a low-purity starting material₃NH₃Br, purity 98%) and 1mmol PbBr₂(lead bromide, 98% purity) was dissolved in 1ml of DMF solvent, and stirring was continued for 1h to give a mixed solution, which was then filtered and transferred to a small beaker. 3ml of diethyl ether is injected into the beaker, stirred for 1 minute, and orange perovskite microcrystal precipitate MAPbBr is separated out at the bottom of the beaker₃. Precipitating the perovskite microcrystal precipitate MAPbBr obtained by precipitation₃Washing with diethyl ether for 3 times, and vacuum drying at normal temperature to remove residual diethyl ether to obtain the perovskite material powder MAPbBr of the embodiment₃The calculated yield was 90%. The perovskite material powder MAPbI prepared by the embodiment₃The XRD diffraction peak positions of the powder photographs are shown in FIG. 6. The XRD pattern shows that the perovskite material powder is of a single crystal form and has no impurity phase.

Example 6:

a low-purity starting material, 0.9mmol MAI (methylamine hydroiodide, CH)₃NH₃I, purity 98%), 0.1mmol CsI (cesium iodide, purity 98%) and 0.8mmol PbI₂(lead iodide, purity 98%) was dissolved in 1ml of γ -butyrolactone solvent, and stirring was continued for 1h to give a mixed solution, which was then filtered and transferred to a small beaker. 2.5ml of diethyl ether is injected into the beaker, and after 30 seconds of stirring, the black perovskite microcrystal precipitate MA is separated out at the bottom of the beaker_0.9Cs_0.1PbI₃. Precipitating the precipitated perovskite microcrystal MA_0.9Cs_0.1PbI₃Washing with diethyl ether for 3 times, and vacuum drying at room temperature to remove residual diethyl ether to obtain the perovskite material powder MA of the embodiment_0.9Cs_0.1PbI₃The calculated yield was 89%.

It should be understood that the structures, ratios, sizes, and the like shown in the drawings and described in the specification are only used for understanding and reading the present disclosure, and are not used for limiting the conditions of the present disclosure, which will not be technically significant, and any structural modifications, ratio changes or size adjustments should fall within the scope of the present disclosure without affecting the function and the achievable purpose of the present disclosure. In addition, the terms "upper", "inner", "outer", "bottom", "one" and "middle" used in the present specification are for convenience of description and are not intended to limit the scope of the present invention, and changes or modifications in the relative relationship may be made without substantial changes in the technical content.