A位La/Sr共掺杂PbZrO3薄膜的制备及储能特性优化

doi:10.15541/jim20240087

无机材料学报 ›› 2024, Vol. 39 ›› Issue (9): 1022-1028.DOI: 10.15541/jim20240087

A位La/Sr共掺杂PbZrO₃薄膜的制备及储能特性优化

沈浩¹(), 陈倩倩¹, 周渤翔¹, 唐晓东¹, 张媛媛¹^,²()

1.华东师范大学电子科学系, 极化材料与器件教育部重点实验室, 上海 200241
2.华东师范大学重庆研究院, 重庆 401120

收稿日期:2024-02-28 修回日期:2024-03-11 出版日期:2024-09-20 网络出版日期:2024-03-30
通讯作者: 张媛媛, 副教授. E-mail: yyzhang@ee.ecnu.edu.cn
作者简介:沈浩(1990-), 男, 硕士研究生. E-mail: sh17855518188@163.com
基金资助:
重庆市自然科学基金(CSTB2022NSCQ-MSX1474)

Preparation and Energy Storage Properties of A-site La/Sr Co-doped PbZrO₃ Thin Films

SHEN Hao¹(), CHEN Qianqian¹, ZHOU Boxiang¹, TANG Xiaodong¹, ZHANG Yuanyuan¹^,²()

1. Key Laboratory of Polar Materials and Devices, Ministry of Education, Department of Electronic Science, East China Normal University, Shanghai 200241, China
2. Chongqing Institute of East China Normal University, Chongqing 401120, China

Received:2024-02-28 Revised:2024-03-11 Published:2024-09-20 Online:2024-03-30
Contact: ZHANG Yuanyuan, associate professor. E-mail: yyzhang@ee.ecnu.edu.cn
About author:SHEN Hao (1990-), male, Master candidate. E-mail: sh17855518188@163.com
Supported by:
Natural Science Foundation of Chongqing Municipality(CSTB2022NSCQ-MSX1474)

摘要/Abstract

摘要：

反铁电材料凭借超高的功率密度, 在电介质能量存储领域具有极高的研究热度。锆酸铅(PbZrO₃, PZO)是反铁电材料的典型代表, 也是研究最为广泛的反铁电材料之一。如何提升PZO基材料的储能性能是目前的研究重点。本工作在La³⁺掺杂PZO的基础上, 进一步将小半径的Sr²⁺掺入到PZO钙钛矿结构的A位, 实现了PZO基反铁电薄膜储能性能的进一步提升。采用溶胶-凝胶法制备了A位La/Sr共掺杂Pb_0.94-_xLa_0.04Sr_xZrO₃(Sr-PLZ-x, x = 0, 0.03, 0.06, 0.09, 0.12)反铁电薄膜, 系统研究了不同Sr²⁺掺杂量对Sr-PLZ-x反铁电薄膜的晶体结构, 以及铁电性能、储能性能和疲劳性能等的影响。结果表明：随着Sr²⁺掺杂量x的增加, Sr-PLZ-x薄膜的晶格常数不断减小, 薄膜的饱和极化强度先略有增加并保持, 后逐渐降低。同时, Sr-PLZ-x薄膜的容忍因子逐步降低, 转折电场不断增大, 反铁电性逐渐增强, 击穿场强有所提高, 储能性能得到提高。在x=0.03时, Sr-PLZ-x反铁电薄膜的储能密度和储能效率分别达到31.7 J/cm³和71%, 储能性能最优。同时掺入Sr²⁺也使得Sr-PLZ-x反铁电薄膜的疲劳性能进一步优化, 其中x=0.12组分薄膜样品在经历了10⁷次循环后, 储能密度和储能效率仅有3.4%和2.7%的衰减。综上所述, A位La/Sr共掺杂可有效提高PZO基反铁电薄膜的储能性能。

关键词: 元素掺杂, 锆酸铅, 反铁电, 储能

Abstract:

Antiferroelectric materials have been extensively studied in the field of dielectric energy storage due to their ultra-high power density. Lead zirconate (PbZrO₃, PZO), as a prototype of antiferroelectric material, has been one of the most studied antiferroelectric materials, and research on enhancing energy storage performance of PZO-based materials is a hotspot of the current study. In this work, further improvement of the energy storage performance of PZO-based antiferroelectric thin films was realized by further doping small-radius Sr²⁺ into the A-site of the PZO perovskite structure on the basis of La³⁺-doped PZO. A series of antiferroelectric thin films of A-site La/Sr co-doped Pb_0.94-_xLa_0.04Sr_xZrO₃ (Sr-PLZ-x, x = 0, 0.03, 0.06, 0.09, 0.12) were prepared by Sol-Gel method, and the effects of Sr²⁺ doping on the crystal structure and electrical properties such as ferroelectricity, energy storage, and fatigue properties of Sr-PLZ-x antiferroelectric films were systematically investigated. The results show that with the doping of Sr²⁺, the lattice constants are gradually reduced, and the saturation polarization of the films is first slightly increased and then maintained, but finally gradually decreased. The tolerance factors of Sr-PLZ-x films are reduced with increasing Sr²⁺ doping content, while the antiferroelectricities of the films are enhanced. Both the switching field and the breakdown strength are increased, resulting in an improved energy storage performance of Sr-PLZ-x films. At x=0.03, the energy storage performance of Sr-PLZ-x antiferroelectric film reaches the highest, with the energy storage density and efficiency are 31.7 J/cm³ and 71%, respectively. Meanwhile, the doping of Sr²⁺ also makes the fatigue characteristics of Sr-PLZ-x antiferroelectric films further improved. The x=0.12 antiferroelectric film exhibits only 3.4% and 2.7% degradation in energy storage density and energy storage efficiency after 10⁷ cycles. In summary, the method of A-site La/Sr co-doping can effectively improve the energy storage performance of PZO-based antiferroelectric films.

Key words: elemental doping, lead zirconate, antiferroelectric, energy storage

中图分类号:

TB34

沈浩, 陈倩倩, 周渤翔, 唐晓东, 张媛媛. A位La/Sr共掺杂PbZrO₃薄膜的制备及储能特性优化[J]. 无机材料学报, 2024, 39(9): 1022-1028.

SHEN Hao, CHEN Qianqian, ZHOU Boxiang, TANG Xiaodong, ZHANG Yuanyuan. Preparation and Energy Storage Properties of A-site La/Sr Co-doped PbZrO₃ Thin Films[J]. Journal of Inorganic Materials, 2024, 39(9): 1022-1028.

图/表 5

图1 在Pt(111)/Ti/SiO2/Si上生长的Sr-PLZ-x薄膜的XRD谱图(a)以及(111)衍射峰附近的XRD放大图(b)

Fig. 1 XRD patterns of Sr-PLZ-x films grown on Pt(111)/Ti/SiO2/Si (a) and enlarged XRD patterns at the (111) diffraction peak (b)

图2 Sr-PLZ-x薄膜样品的SEM截面照片

Fig. 2 Cross-section SEM images of Sr-PLZ-x thin films (a) x=0; (b) x=0.03; (c) x=0.06; (d) x=0.09; (e) x=0.12

图3 Sr-PLZ-x薄膜样品的P-E回线和相应I-E曲线(a~e)以及转折电场EAF、EFA随Sr2+掺杂量的变化关系(f)

Fig. 3 P-E hysteresis loops and I-E curves of Sr-PLZ-x thin films (a-e) and switching fields EAF and EFA as a function of Sr2+ doping content (f) Colorful figures are available on website

图4 Sr-PLZ-x薄膜样品的储能性能

Fig. 4 Energy-storage properties of Sr-PLZ-x thin films (a, b) Variations of (a) EBDS, (b) Wre and η with Sr2+ doping content; (c) Wre and (d) η of Sr-PLZ-x thin films measured at different electric fields

图5 Sr-PLZ-x薄膜样品的疲劳特性

Fig. 5 Fatigue properties of Sr-PLZ-x thin films (a) x=0; (b) x=0.03; (c) x=0.06; (d) x=0.09; (e) x=0.12

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A位La/Sr共掺杂PbZrO₃薄膜的制备及储能特性优化

Preparation and Energy Storage Properties of A-site La/Sr Co-doped PbZrO₃ Thin Films

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