CN109824086B - Na-doped Cs2SbAgCl6Preparation method of double-layer perovskite nano material - Google Patents
Na-doped Cs2SbAgCl6Preparation method of double-layer perovskite nano material Download PDFInfo
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Abstract
The Na-doped Cs of the invention2SbAgCl6A preparation method of a double-layer perovskite nano material belongs to the technical field of semiconductor nano material preparation. Weighing cesium chloride, silver chloride, sodium chloride and antimony trichloride according to a molar ratio of 6:2:1:3, mixing, adding into a ball milling tank which is paved with grinding balls, installing the ball milling tank, and then putting into a ball mill for ball milling for 3 hours to obtain Na: Cs2SbAgCl6Double-layer perovskite nano material. The method has the advantages of mild conditions, simple operation, short reaction time, easy industrial production and the like, and the synthesized Na: Cs2SbAgCl6The double-layer perovskite nano material has higher fluorescence quantum efficiency.
Description
Technical Field
The invention belongs to the technical field of semiconductor nano material preparation, and relates to Na-doped Cs which is efficient, stable and simple and controllable in operation method2SbAgCl6A preparation method of a double-layer perovskite nano material.
Background
In recent years, perovskite nanomaterials, particularly lead perovskite halide nanomaterials, are made to stand out in the application of solar cells, LEDs, lasers and photodetectors due to their excellent charge transport properties and good chemical controllability, and particularly in the field of solar cells, the photoelectric conversion efficiency of the perovskite nanomaterials can reach 20%, so that the lead perovskite halide has been widely studied.
However, although lead-perovskite halides have good electronic properties and are relatively inexpensive to produce for photovoltaic and photovoltaic applications, their stability and their health and environmental concerns continue to hinder their commercial development. The use of lead-containing electrical equipment has been clearly regulated in most countries and therefore the development of lead-free and pure inorganic perovskite materials has made a great deal of effort to overcome the toxicity and stability problems of lead halides.
Published reports have focused primarily on pure inorganic CsPbX3Perovskite nanomaterials, the general formula for recently studied perovskite materials being ABX3 (A=Cs2+,B = Pb2+Or Sn2+,X = Cl−,Br−,I−). An important property of these compounds is their bandgap tunability, achieved by varying the species A, B and X.
Recent studies have shown that to maintain valence state and structural coordination number, B1+And B3+Substitution for Pb2+In ABX3Of [111 ]]The creation of a voided layer in the direction to maintain charge neutrality forms a double-layered perovskite. A formed by trivalent cation combination (B ') and monovalent (B') cation combination replacing B region2B’B”X6Double layer perovskite, simulated ABX3The perovskite structure shows the improvement of the stability to air and moisture, and has wide applicability in solar cells. However, such double-layer perovskites generally have low fluorescence yield, which hinders their application to optoelectronic devices. We therefore assume that this material would be better served to humans if the fluorescence yield of the double-layer perovskite could be increased while maintaining its good stability.
Cs is successfully synthesized by Deng et al in 20172SbAgCl6The band gap is indirect and the band gap value is 2.6eV, the quantum yield of the method reported in the literature is low, and the method is liquid phase synthesis, but the method requires severe conditions and needs to be carried out in a solution at a higher temperature, the temperature rising or reducing rate in the reaction has great influence on the particle size of the final product, and the reaction time of the liquid phase synthesis is generally as long as 24 hours.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the background technology and provide a catalyst which can be synthesized in large quantity at normal temperature and normal pressureNovel method for synthesizing Na-doped Cs2SbAgCl6Double-layer perovskite nano material.
The technical problem of the invention is solved by the following technical scheme:
na-doped Cs2SbAgCl6The preparation method of the double-layer perovskite nano material comprises the steps of weighing cesium chloride, silver chloride, sodium chloride and antimony trichloride according to the molar ratio of 6:2:1:3, mixing, adding into a ball milling tank which is paved with grinding balls, installing the ball milling tank, and then putting into a ball mill for ball milling for 3 hours to obtain Na: Cs2SbAgCl6Double-layer perovskite nano material.
Preferably, the diameter of the grinding ball is 6mm, the rotation frequency of the ball mill is 40Hz, and the forward and reverse directions are alternately operated.
Has the advantages that:
the invention realizes Na-Cs by mechanical grinding2SbAgCl6The method has mild conditions, simple operation, short reaction time and easy industrial production, and the synthesized Na: Cs2SbAgCl6The double-layer perovskite nano material has higher fluorescence quantum efficiency.
Description of the drawings:
FIG. 1 is Cs prepared in example 12SbAgCl6Double-layer perovskite nano material and Na-Cs2SbAgCl6The emission spectrum of the double-layer perovskite nano material.
FIG. 2 shows Na: Cs prepared in example 12SbAgCl6XRD pattern of double-layer perovskite nano material.
FIG. 3 is Cs prepared in example 22SbAgCl6XRD pattern of double-layer perovskite nano material.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
Which are given by way of illustration only and are not to be construed as limiting the present patent.
Example 1: preparation of Na: Cs2SbAgCl6Double-layer perovskite nano material
Can taking containerA50 ml ball mill pot was filled with a layer of 6mm diameter balls (about 15 balls) and m (CsCl): m (AgCl + NaCl): m (SbCl) was calculated according to the molar ratio of the formula3) And (5) weighing 2 mmol (0.337 g) of cesium chloride powder, 0.66 mmol (0.096 g) of silver chloride solid, 0.33mmol (0.0132g) of sodium chloride solid and 1mmol (0.228 g) of antimony trichloride solid, putting the cesium chloride powder, 0.66 mmol (0.096 g) of silver chloride solid, 0.33mmol (0.0132g) of sodium chloride solid and 1mmol (0.228 g) of antimony trichloride solid into a ball mill pot of a model QM-3SP04, hanging a puller in a ball mill tray after the pot filling is finished, firstly, tightly pressing by rotating a hand wheel, then, forcibly screwing a claw and screwing a cap to prevent the ball mill pot from loosening and causing accidents when the ball mill is operated, covering a protective cover after the ball mill pot is mounted, setting the rotation frequency to be 40Hz, operating for 180 minutes by adopting a positive and reverse alternating operation mode, dismounting the puller and the ball mill pot after the ball milling is finished, pouring a sample and grinding balls into the sieve, and separating the grinding materials. The finally separated substance is the synthesized Na-Cs2SbAgCl6The emission spectrum of the double-layer perovskite nano material is shown in figure 1, and the XRD diffraction spectrum thereof is shown in figure 2. The fluorescence quantum efficiency is as follows: 24.8 percent.
Example 2: comparative example without Na doping
Taking a ball milling tank with a tank volume of 50ml, flatly laying and filling a layer of grinding balls (about 15 grains) with the diameter of 6mm, and calculating m (CsCl): m (AgCl): m (SbCl) according to the molar ratio of the chemical formula3) Weighing 2 mmol (0.337 g) of cesium chloride powder, 1mmol (0.144 g) of silver chloride solid and 1mmol (0.228 g) of antimony trichloride solid, putting the weighed cesium chloride powder, 1mmol (0.144 g) of silver chloride solid and 1mmol (0.228 g) of antimony trichloride solid into a ball milling tank with the model of QM-3SP04, putting the ball milling tank into a ball mill tray, hanging a puller on the ball mill tray after the completion of the canning, firstly, tightly pressing the ball milling tank by rotating a hand wheel, then, forcibly rotating a goat horn to tighten the ball and a cap to prevent the ball milling tank from loosening and causing accidents during the operation of the ball mill, covering a protective cover on the ball milling tank after the completion of the installation, setting the rotation frequency to be 40Hz, operating for 180 minutes by adopting a forward and reverse alternate operation mode of stopping the machine at regular time, unloading the puller and the ball milling tank after the completion of the ball milling, pouring a sample and grinding balls into a sieve, and separating the grinding materials. The light yellow solid powder obtained by final separation is the synthesized Cs2SbAgCl6The emission spectrum of the double-layer perovskite nano material is shown in figure 1, and the XRD diffraction spectrum thereof is shown in figure 3. The fluorescence quantum efficiency is less than 1%.
The preparation method has the advantages of mild conditions, simple operation and short reaction time. And the invention is in preparing Cs2SbAgCl6Na doping is also carried out during the double-layer perovskite nano material, and after sodium doping, the fluorescence quantum efficiency is obviously improved.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (2)
1. Na-doped Cs2SbAgCl6The preparation method of the double-layer perovskite nano material comprises the steps of weighing cesium chloride, silver chloride, sodium chloride and antimony trichloride according to the molar ratio of 6:2:1:3, mixing, adding into a ball milling tank which is paved with grinding balls, installing the ball milling tank, and then putting into a ball mill for ball milling for 3 hours to obtain Na: Cs2SbAgCl6Double-layer perovskite nano material.
2. The Na-doped Cs of claim 12SbAgCl6The preparation method of the double-layer perovskite nano material is characterized in that the diameter of a grinding ball is 6mm, the rotation frequency of a ball mill is 40Hz, and the ball mill runs in a forward direction and a reverse direction alternately.
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| CN111073637B (en) * | 2019-12-03 | 2021-09-07 | 北京理工大学 | Zero-dimensional lead-free perovskite fluorescent material, and preparation and application thereof |
| CN110938428B (en) * | 2019-12-03 | 2021-08-31 | 吉林大学 | High-efficiency synthetic Cs2AgCl3Method for preparing all-inorganic non-lead perovskite |
| CN111139068A (en) * | 2019-12-03 | 2020-05-12 | 北京理工大学 | Zero-dimensional lead-free perovskite Cs3Cu2X5Preparation method and application of |
| CN113697855B (en) * | 2020-05-20 | 2022-07-12 | 中国科学院上海硅酸盐研究所 | Cu-doped double perovskite material and preparation method thereof |
| CN116790247A (en) * | 2023-04-20 | 2023-09-22 | 安顺学院 | Preparation method of all-inorganic lead-free halide multicolor luminescent fluorescent powder, product and application thereof |
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| CN108028320A (en) * | 2015-09-02 | 2018-05-11 | 牛津大学科技创新有限公司 | double-perovskite |
| CN108659827A (en) * | 2018-06-15 | 2018-10-16 | 华中科技大学 | Near ultraviolet excitated double-perovskite single-substrate white fluorescent material and preparation and application |
| WO2018231909A1 (en) * | 2017-06-13 | 2018-12-20 | Board Of Trustees Of Michigan State University | Method for fabricating epitaxial halide perovskite films and devices |
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| CN108028320A (en) * | 2015-09-02 | 2018-05-11 | 牛津大学科技创新有限公司 | double-perovskite |
| WO2018231909A1 (en) * | 2017-06-13 | 2018-12-20 | Board Of Trustees Of Michigan State University | Method for fabricating epitaxial halide perovskite films and devices |
| CN108659827A (en) * | 2018-06-15 | 2018-10-16 | 华中科技大学 | Near ultraviolet excitated double-perovskite single-substrate white fluorescent material and preparation and application |
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