阅读说明：本技术 一种二维银铋卤化物双钙钛矿材料及合成和应用 (Two-dimensional silver bismuth halide double perovskite material and synthesis and application thereof ) 是由 韩克利 程鹏飞 赵文远 于 2019-10-16 设计创作，主要内容包括：本发明公开了一种二维银铋卤化物双钙钛矿材料,其步骤包括将溴化苯乙胺、含银化合物、含铋化合物加入到氢溴酸的水溶液中,混合物在氮气保护下100℃～120℃搅拌3～5h；反应结束后,冷却至室温,快速抽滤,将得到的晶体放入真空烘箱中60℃～80℃保持18～24h。本发明制备方法简单,得到的二维钙钛矿环保无毒且非常稳定,在光伏领域具有良好的应用前景。(The invention discloses a two-dimensional silver bismuth halide double perovskite material which comprises the steps of adding phenylethylamine bromide, a silver-containing compound and a bismuth-containing compound into an aqueous solution of hydrobromic acid, and stirring the mixture for 3-5 hours at 100-120 ℃ under the protection of nitrogen; and after the reaction is finished, cooling to room temperature, quickly performing suction filtration, and putting the obtained crystal into a vacuum oven to be kept at 60-80 ℃ for 18-24 h. The preparation method is simple, and the obtained two-dimensional perovskite is environment-friendly, non-toxic and very stable, and has good application prospect in the photovoltaic field.)

1. A two-dimensional silver bismuth halide double perovskite material, wherein the two-dimensional silver bismuth halide double perovskite material has a chemical formula of (PEA)₄AgBiBr₈Wherein PEA is phenethylamine (C)₆H₅CH₂CH₂NH₂) The two-dimensional perovskite structure is formed by sequentially and alternately forming organic phenethylamine layers and inorganic silver bromide and bismuth bromide mixed layers, the layers are connected by Van der Waals force, and the interlayer spacing is 1.64 nm.

2. A two-dimensional silver bismuth halide double perovskite material as claimed in claim 1, wherein: the thickness of the organic layer was 1.03nm and the thickness of the inorganic layer was 0.61 nm.

3. A two-dimensional silver bismuth halide double perovskite material as claimed in claim 1, wherein: the material can be stable in air for more than one year.

4. A method of synthesizing a two-dimensional silver bismuth halide double perovskite material as claimed in any one of claims 1 to 3, wherein the steps are carried out as follows:

firstly, the bromophenylethylamine (C) is added according to the required metering ratio₆H₅CH₂CH₂NH₃Br), a silver-containing compound and a bismuth-containing compound are added into an aqueous solution of hydrobromic acid, and the mixture is stirred for 3-5 h at 100-120 ℃ under the protection of nitrogen;

and (II) after the reaction is finished, cooling to room temperature, carrying out suction filtration, and placing the obtained crystal into a vacuum oven to be kept at the temperature of 60-80 ℃ for 18-24 h.

5. The method for synthesizing a two-dimensional silver bismuth halide double perovskite material as claimed in claim 4, wherein: the silver-containing compound used in the preparation process is one or more than two of silver iodide, silver bromide or silver carbonate.

6. The method for synthesizing a two-dimensional silver bismuth halide double perovskite material as claimed in claim 4, wherein: the bismuth-containing compound used in the preparation process is one or more than two of bismuth iodide, bismuth bromide or bismuth oxide.

7. The method for synthesizing a two-dimensional silver bismuth halide double perovskite material as claimed in claim 4, wherein: the preparation process comprises the following steps: 1mmol (PEA) per synthesis₄AgBiBr₈15-20 ml of 47.0-49.0 wt.% aqueous hydrobromic acid solution are required.

8. Use of a two-dimensional silver bismuth halide double perovskite material as defined in any one of claims 1 to 3, wherein: the optical band gap of the material is 2.61eV, and the material can be used as a light absorption material and is suitable for a light absorption layer of a solar cell.

Technical Field

The invention belongs to the technical field of solar cells, and particularly relates to a novel solar cell material, synthesis and application.

Background

The two-dimensional organic-inorganic hybrid perovskite material has unique photoelectric properties and excellent stability, and has become a research hotspot in the field of materials. Although hundreds of two-dimensional organic-inorganic hybrid perovskite materials have been reported, most are based on a limited number of divalent cations, such as Pb²⁺、Cu²⁺、Mn²⁺、Cr²⁺、Sn²⁺、Cd²⁺And the like. In contrast, double perovskites contain an ordered arrangement of two different metal cations, which can accommodate more different metals and oxidation states, helping to extend the range of two-dimensional perovskite materials, but few reports on two-dimensional halide double perovskite materials are currently available.

Disclosure of Invention

The invention aims to provide a two-dimensional silver bismuth halide double perovskite material and a preparation method thereof, the material is simple to prepare, environment-friendly, nontoxic and excellent in photoelectric property, and is expected to be used for photoelectric devices such as solar cells.

A two-dimensional silver bismuth halide double perovskite material, wherein the two-dimensional silver bismuth halide double perovskite material has the chemical formula (PEA)₄AgBiBr₈PEA is phenethylamine (C)₆H₅CH₂CH₂NH₂) The two-dimensional perovskite structure is formed by sequentially and alternately forming organic phenethylamine layers and inorganic silver bromide/bismuth bromide mixed layers, the layers are connected by Van der Waals force, and the interlayer spacing is 1.64 nm.

The preparation method of the two-dimensional silver bismuth halide double perovskite material comprises the following steps:

adding the brominated phenethylamine, the silver-containing compound and the bismuth-containing compound into a hydrobromic acid solution according to the required metering ratio, heating and stirring the mixture for 3-5 h at 100-120 ℃ under the protection of nitrogen, and obtaining a golden yellow transparent solution. And after the reaction is finished, cooling to room temperature, performing suction filtration, and putting the obtained crystal into a vacuum oven to be kept at the temperature of 60-80 ℃ for 18-24 h. The components of the product are detected by an energy dispersive X-ray spectrometer, wherein the atomic ratio of silver to bismuth is 1: 1.

The synthesis method of the two-dimensional silver bismuth halide double perovskite material is characterized in that a silver-containing compound used in the preparation process is one or more than two of silver iodide, silver bromide or silver carbonate.

The synthesis method of the two-dimensional silver bismuth halide double perovskite material is characterized in that the bismuth-containing compound used in the preparation process is one or more than two of bismuth iodide, bismuth bromide or bismuth oxide.

The synthesis method of the two-dimensional silver bismuth halide double perovskite material comprises the following steps: 1mmol (PEA) per synthesis₄AgBiBr₈15 to 20ml of 48 wt.% aqueous hydrobromic acid solution were required.

The optical band gap of the two-dimensional silver bismuth halide double perovskite material is detected to be 2.61eV through solid-ultraviolet absorption spectrum, and the two-dimensional silver bismuth halide double perovskite material can be used as a light absorption material and is suitable for being used in a light absorption layer of a solar cell.

The crystal structure of the two-dimensional silver bismuth halide double perovskite material is kept unchanged through X-ray diffraction detection, and the two-dimensional silver bismuth halide double perovskite material can be stable in the air for more than one year.

Has the advantages that:

the preparation method is simple, and the obtained two-dimensional perovskite is environment-friendly, non-toxic and very stable, and has good application prospect in the photovoltaic field.

The invention provides an environment-friendly and nontoxic two-dimensional silver bismuth halide double perovskite material which has a proper absorption spectrum range and excellent stability and has a good photoelectric application prospect.

Drawings

FIG. 1 is a powder XRD diffraction pattern and a scanning electron microscope image of a single crystal of a two-dimensional silver bismuth halide double perovskite material of the invention.

FIG. 2 is an ultraviolet-visible absorption spectrum of a two-dimensional silver bismuth halide double perovskite material of the invention.

Detailed Description

The invention is further described with reference to the accompanying drawings and specific embodiments:

example 1

808.4mg of phenethylamine bromide, 187.6mg of silver bromide and 233.0mg of bismuth oxide were added to 15ml of an aqueous hydrobromic acid (48 wt.%), and the mixture was stirred at 100 ℃ for 5h under nitrogen. After the reaction is finished, cooling to room temperature, quickly performing suction filtration, and putting the obtained crystal into a vacuum oven to keep the temperature at 70 ℃ for 24 hours.

Through powder XRD diffraction test and scanning electron microscope observation, as shown in figure 1, the obtained two-dimensional silver bismuth halide double perovskite material has high crystallinity and an obvious layered structure. The two-dimensional perovskite structure is formed by alternating organic phenethylamine layers and inorganic silver bromide/bismuth bromide mixed layers, the layers are connected by Van der Waals force, the interlayer spacing is 1.64nm, the thickness of the organic layer is 1.03nm, and the thickness of the inorganic layer is 0.61 nm.

EXAMPLE 2

808.4mg of phenethylamine bromide, 275.8mg of silver carbonate and 448.7mg of bismuth bromide were added to 20ml of an aqueous solution of hydrobromic acid (48 wt.%), and the mixture was stirred at 120 ℃ for 4h under nitrogen. After the reaction is finished, cooling to room temperature, quickly performing suction filtration, and putting the obtained crystal into a vacuum oven to keep the temperature of 80 ℃ for 20 hours.

UV-visible absorption test (reference 1: Cheng P F, Wu T, Han K L, et al (C.)₆H₅C₂H₄NH₃)₂GeI₄:A Layered Two-Dimensional Perovskite with Potential for Photovoltaic Applications[J]J.Phys.chem.Lett.2017,8, 4402-4406. ) As shown in fig. 2, the obtained two-dimensional silver bismuth halide double perovskite material has a certain width of absorption spectrum in the visible light range.

The above-mentioned embodiments are merely preferred embodiments of the present invention, which are merely illustrative and not restrictive, and all technical solutions obtained by means of equivalents and equivalent changes fall within the protection scope of the present invention.