爆炸冲击合成铯铅氯钙钛矿粉体

doi:10.12382/bgxb.2024.0339

摘要/Abstract

摘要：

金属卤化物钙钛矿具有优异的光电性能和极具潜力的应用价值,成为目前研究热点之一,钙钛矿材料的元素组成及晶体结构对其性能有重要影响。为实现新型钙钛矿制备,开展冲击加载制备铯铅氯(CsPbCl₃)钙钛矿研究。采用爆轰驱动飞片的冲击加载方式,在0.6~0.8的致密度、14.2~27.9GPa的冲击压力条件下实现了CsPbCl₃钙钛矿粉末的冲击合成。X射线衍射仪、扫描电子显微镜、透射电子显微镜等多种分析表征结果表明回收产物为CsPbCl₃钙钛矿粉末。实验结果表明,冲击压力与前体粉末致密度是合成CsPbCl₃钙钛矿粉末的2个关键因素。结合实验条件与分析表征结果,对CsPbCl₃的合成进行了机理分析,发现当冲击压力在14~17GPa范围内时,可以合成高纯度的CsPbCl₃粉体,没有非化学计量比产物形成,表明冲击合成法是一种制备难合成钙钛矿的可行方法。

关键词: CsPbCl₃钙钛矿, 冲击合成, 爆轰驱动飞片, 冲击波

Abstract:

Metal halide perovskites have become a current research hotspot owing to their exceptional optoelectronic properties and significant potential application value. The elemental composition and crystal structure of perovskite material have crucial influence on its performance.To realize the preparation of novel perovskites,this paper focuses on the research of synthesizing cesium lead chloride perovskite (CsPbCl₃) under shock loading.In this study,CsPbCl₃ perovskite powder is synthesized by the shock loading of detonation-driven flyer plates under the conditions of 0.6-0.8 relative densities of powder and 14.2-27.9GPa shock pressures.The characterization results of X-ray diffraction (XRD),scanning electron microscopy (SEM) and transmission electron microscopy (TEM) indicate that the recovered products are CsPbCl₃ perovskite powders.Experimental results also demonstrate that the shock pressure and the relative density of precursor are two key factors to the synthesis of CsPbCl₃ perovskite powder.Based on the experimental conditions and analytical characterization results,a formation mechanism of CsPbCl₃ synthesis is discussed.It is confirmed that the proper shock pressure for high-purity CsPbCl₃ powder synthesis is from 14GPa to 17GPa.It is also suggested that the shock synthesis method is a feasible approach for preparing difficult-to-synthesize perovskite.

Key words: CsPbCl₃ perovskite, shock synthesis, detonation-driven flyer plate, shock wave

中图分类号:

TJ301

肖泽琦, 高鑫, 张雪迎, 刘开源, 岳丽丹, 秦智奇, 陈鹏万. 爆炸冲击合成铯铅氯钙钛矿粉体[J]. 兵工学报, 2025, 46(3): 240339-.

XIAO Zeqi, GAO Xin, ZHANG Xueying, LIU Kaiyuan, YUE Lidan, QIN Zhiqi, CHEN Pengwan. Explosive Shock Synthesis of Cesium Lead Chloride Perovskite Powder[J]. Acta Armamentarii, 2025, 46(3): 240339-.

图/表 14

图1 冲击压缩装置

Fig.1 Schematic diagram of shock compression device

表1 实验条件

Table 1 Experimental conditions

编号	致密度	爆速/ (m·s^-1)	飞片厚度/mm	装药高度/mm	飞片速度/ (km·s^-1)	冲击压力/ GPa
1-1	0.6	2100	1	70	1.04	14.2
1-2	0.7					15.6
1-3	0.8					17.2
2-1	0.6	2300	1	100	1.28	17.9
2-2	0.7					19.6
2-3	0.8					21.6
3-1	0.6	2600	1	100	1.45	20.7
3-2	0.7					22.6
3-3	0.8					24.9
4-1	0.6	3200	1	70	1.59	23.3
4-2	0.7					25.4
4-3	0.8					27.9
5-2	0.7	2600	1	80	1.35	21.0

图2 冲击压力与粒子速度

Fig.2 Shock pressure and particle velocity

表2 阻抗匹配法计算压力所用参数

Table 2 Calculation of pressure parameters by impedance matching method

材料	致密度	密度/ (g·cm^-3)	Hugoniot参数
材料	致密度	密度/ (g·cm^-3)	C/(km·s^-1)	S
CsCl+PbCl₂	0.6	4.97	3.3796	1.0685
	0.7		4.0484
	0.8		4.8695

图3 实验原料、研磨后的混合粉末以及回收产物的XRD图谱

Fig.3 XRD patterns of raw materials,grounded mixed powder and recovered products

图4 不同压力下产物的XRD图谱

Fig.4 XRD patterns of products under different shock pressures

表3 不同实验条件下回收产物的晶粒尺寸

Table 3 Grain sizes of recovered products under different experimental conditions

编号	致密度	冲击压力/GPa	晶粒尺寸/nm
4-1	0.6	23.3	49.2
3-1		20.7	50.4
2-1		17.9	54.0
1-1		14.2	61.9
4-2	0.7	25.4	45.6
3-2		22.6	44.7
2-2		19.6	51.8
1-2		15.6	80.9
4-3	0.8	27.9	45.2
3-3		24.9	38.9
2-3		21.6	54.2
1-3		17.2	61.8

图5 相同压力、不同致密度下回收产物的XRD图谱

Fig.5 XRD patterns of products under the same shock pressure and different relative densities

表4 相同压力下CsPbCl3与Cs4PbCl6的XRD衍射峰峰强比

Table 4 Peak intensity ratio of CsPbCl3 and Cs4PbCl6 under the same shock pressure

编号	致密度	冲击压力/ GPa	Cs₄PbCl₆:CsPbCl₃ 相对峰强/%
2-3	0.8	21	8.01
5-2	0.7		7.54
3-1	0.6		11.02

图6 1-3号样品的EDS图像(上为扫描区域,下为扫描结果)

Fig.6 EDS images of Products 1-3(The top is the scan area,and the bottom is the scan results)

表5 EDS数据结果

Table 5 EDS results

元素及总量	原子质量百分比/%
Cl	61.07
Cs	21.02
Pb	17.91
总量	100.00

图7 SEM图像

Fig.7 SEM images

图8 TEM图像(左为形貌图,右为相应的高分辨图像)

Fig.8 TEM images(The left is the morphology image,and the right is the corresponding high-resolution image)

图9 产物3-1的高分辨图像和IFFT图像

Fig.9 High resolution image and IFFT image of Product 3-1

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