0.9BaTiO3-0.1Bi(Mg1/2Ti1/2)O3铁电薄膜制备及储能特性

doi:10.15541/jim20230488

无机材料学报 ›› 2024, Vol. 39 ›› Issue (3): 291-298.DOI: 10.15541/jim20230488 CSTR: 32189.14.10.15541/jim20230488

所属专题：【信息功能】介电、铁电、压电材料（202409）；【信息功能】纪念殷之文先生诞辰105周年虚拟学术专辑

0.9BaTiO₃-0.1Bi(Mg_1/2Ti_1/2)O₃铁电薄膜制备及储能特性

刘松¹^,²(), 张发强², 罗进¹(), 刘志甫²()

1.南京工业大学材料科学与工程学院, 材料化学工程国家重点实验室, 南京 210009
2.中国科学院上海硅酸盐研究所, 上海 200050

收稿日期:2023-10-20 修回日期:2023-11-20 出版日期:2024-03-20 网络出版日期:2023-12-19
通讯作者: 罗进, 副教授. E-mail: jluuky2014@njtech.edu.cn;
刘志甫, 研究员. E-mail: liuzf@mail.sic.ac.cn
作者简介:刘松(1999-), 男, 硕士研究生. E-mail: 202161203172@njtech.edu.cn
基金资助:
国家自然科学基金(51902155);江苏高校优势学科建设工程资助项目;国家重点研发计划项目(2021YFB3800604)

0.9BaTiO₃-0.1Bi(Mg_1/2Ti_1/2)O₃ Ferroelectric Thin Films: Preparation and Energy Storage

LIU Song¹^,²(), ZHANG Faqiang², LUO Jin¹(), LIU Zhifu²()

1. The State Key Laboratory of Materials-Oriented Chemical Engineering, College of Materials Science and Engineering, Nanjing Tech University, Nanjing 210009, China
2. CAS Key Laboratory of Inorganic Functional Materials and Devices, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China

Received:2023-10-20 Revised:2023-11-20 Published:2024-03-20 Online:2023-12-19
Contact: LUO Jin, associate professor. E-mail: jluuky2014@njtech.edu.cn;
LIU Zhifu, professor. E-mail: liuzf@mail.sic.ac.cn
About author:LIU Song (1999-), male, Master candidate. E-mail: 202161203172@njtech.edu.cn
Supported by:
National Natural Science Foundation of China(51902155);Priority Academic Program Development of Jiangsu Higher Education Institutions;National Key Research and Development Program of China(2021YFB3800604)

摘要/Abstract

摘要：

电介质薄膜是通过介质极化方式存储静电能的一种材料, 以其高功率密度和高充放电效率, 在电子器件领域得到广泛应用。目前, 储能密度较低和温度稳定性差仍是电介质储能薄膜的缺陷。本研究采用溶胶-凝胶法在Pt/Ti/SiO₂/Si衬底上制备了0.9BaTiO₃-0.1Bi(Ti_1/2Mg_1/2)O₃(0.9BT-0.1BMT)薄膜, 通过引入BMT期望获得高储能密度及宽温度稳定性, 并研究了退火温度对薄膜的相组成和微观形貌的影响。研究结果表明, 退火温度过高会导致薄膜的致密性明显降低并伴随晶粒尺寸增大, 750 ℃是最佳的退火温度。综合性能研究发现, 1 kHz下, 薄膜的室温介电常数为399, 介电损耗为5.8%。薄膜在各测试频率下的介电温度稳定性满足X9R标准, ∆C/C_{25 ℃}≤±13.9%。通过Currie-Weiss关系计算得到薄膜的弛豫系数(Relaxor value)γ值为≈1.96, 说明其具有明显的弛豫特性。储能特性研究显示, 薄膜的室温储能密度W_rec达51.9 J/cm³, 室温~200 ℃的宽温度范围内, 储能密度W_rec>20 J/cm³, 可释放能量效率η>65%(1600 kV/cm)。在脉冲放电测试中, 薄膜的脉冲放电时间τ_0.9保持在15 μs以内, 且具有优异的频率、温度和循环可靠性。本研究所制备的0.9BT-0.1BMT铁电薄膜具有出色的储能特性和宽温度稳定性, 具备在高温环境中应用的潜力。

关键词: BaTiO₃, 铁电薄膜, 退火温度, 能量存储, 宽温稳定, 弛豫铁电

Abstract:

Dielectric thin film, one of the materials of which storage energy in the form of electrostatic field via dielectric polarization, can be widely used in electric equipment, due to their high power density and high charge/ discharge efficiency. Currently, the dielectric energy storage films perform lower energy density and weak temperature stability. In this work, 0.9BaTiO₃-0.1Bi(Mg_1/2Ti_1/2) O₃(0.9BT-0.1BMT) ferroelectric thin films were prepared via a Sol-Gel method on Pt/Ti/SiO₂/Si substrates and annealed in the range of 700-900 ℃ to realize high energy storage density and wide-temperature stability by introducing BMT. The effect of annealing temperature on phase composition and microstructure was investigated. The results show that denseness of thin films reduce obviously when the annealing temperature is over 750 ℃ and their grain size increases gradually with the increase of treatment temperature. Additionally, the thin films annealed at 750 ℃ display optimized comprehensive feature: room-temperature dielectric constant of ~399, loss tangent of ~5.79% at 1 kHz, and ∆C/C_{25 ℃} ratio only within ±13.9%. Meanwhile, relaxor value, γ≈1.96 calculated according to Currie-Weiss law consolidates that the thin films possess obvious relaxor characteristics. Results of energy storage shows that the max value of W_recis ~ 51.9 J/cm³, and the τ_0.9 is below 15 μs at pulse charge measure. Moreover, results of temperature stability measurement show W_rec>20 J/cm³, η>65% (1600 kV/cm) and τ_0.9<7.2 μs from room temperature to 200 ℃, demonstrating that the film still exists high and stable energy storage under high temperature. Therefore, the ferroelectric thin film 0.9BT-0.1BMT prepared in this work has a promising applications in energy storage under high temperature environment.

Key words: BaTiO₃, ferroelectric thin film, annealing temperature, energy storage, wide-temperature stability, relaxor ferroelectric

中图分类号:

TQ174

刘松, 张发强, 罗进, 刘志甫. 0.9BaTiO₃-0.1Bi(Mg_1/2Ti_1/2)O₃铁电薄膜制备及储能特性[J]. 无机材料学报, 2024, 39(3): 291-298.

LIU Song, ZHANG Faqiang, LUO Jin, LIU Zhifu. 0.9BaTiO₃-0.1Bi(Mg_1/2Ti_1/2)O₃ Ferroelectric Thin Films: Preparation and Energy Storage[J]. Journal of Inorganic Materials, 2024, 39(3): 291-298.

图/表 7

图1 不同温度退火处理0.9BT-0.1BMT薄膜的XRD图谱

Fig. 1 XRD patterns of 0.9BT-0.1BMT thin films annealed at different temperatures

图2 不同温度退火制备的0.9BT-0.1BMT薄膜的SEM照片

Fig. 2 SEM images of thin films annealed at different temperatures (a) 700 ℃; (b) 750 ℃; (c) 800 ℃; (d) 850 ℃; (e) 900 ℃; (f) Cross-section structure of thin films annealed at 750 ℃

图3 750 ℃退火制备的0.9BT-0.1BMT薄膜在不同测试频率下的介电特性

Fig. 3 Dielectric properties of 0.9BT-0.1BMT thin films annealed at 750 ℃ and tested at different frequencies (a-c) Temperature-dependent (a) dielectric constant, (b) loss tangent and (c) capacitance of 0.9BT-0.1BMT thin films annealed at 750 ℃; (d) Function of ln(1/εr−1/εm) versus ln(T−Tm) measured under 1 kHz with symbols standing for experiment data and solid line indicating fitting to the modified Curie-Weiss law

图4 室温下测试的0.9BT-0.1BMT薄膜的电学性能

Fig. 4 Electrical performance of 0.9BT-0.1BMT thin films tested at room temperature (a) P-E loops; (b) Pmax and Pr measured at different electric fields; (c) Wrec and η measured at different electric fields; (d) Leakage current of thin films at 400 kV/cm

图5 本研究制备的材料与其他材料的性能对比

Fig. 5 Property comparison for materials prepared in this work with other materials (a) Energy storage performance [26⇓⇓⇓⇓⇓⇓-33]; (b) Meet ∆C/C25℃≤±15% temperature range[10-11,26]

图6 (a~c)频率、(d~f)温度和(g~i)循环次数对0.9BT-0.1BMT薄膜的P-E曲线、Pmax、Pr和储能特性的影响

Fig. 6 Effects of (a-c) frequency, (d-f) temperature and (g-i) switching cycles on P-E loops, Pmax, Pr, and energy storage performance of 0.9BT-0.1BMT thin films

图7 0.9BT-0.1BMT薄膜电容器的放电特性

Fig. 7 Discharge characteristics of 0.9BT-0.1BMT film capacitors (a) Curves of overdamped discharge current; (b) Time dependence of Wdis at various electric fields; (c) Values of Wdis and τ0.9 at different electric fields; (d) Overdamped discharge current curves at 1388 kV/cm with different temperatures; (e) Time dependence of Wdis at different temperatures; (f) Values of Wdis and τ0.9 at different temperatures; Colorful figures are available on website

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0.9BaTiO₃-0.1Bi(Mg_1/2Ti_1/2)O₃铁电薄膜制备及储能特性

0.9BaTiO₃-0.1Bi(Mg_1/2Ti_1/2)O₃ Ferroelectric Thin Films: Preparation and Energy Storage

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