(0.96NaNbO3-0.04CaZrO3)-xFe2O3反铁电陶瓷的介电及储能性能研究

doi:10.15541/jim20210402

无机材料学报 ›› 2022, Vol. 37 ›› Issue (5): 499-506.DOI: 10.15541/jim20210402

所属专题：【信息功能】电介质材料；【能源环境】钙钛矿

(0.96NaNbO₃-0.04CaZrO₃)-xFe₂O₃反铁电陶瓷的介电及储能性能研究

叶芬¹^,²(), 江向平¹(), 陈云婧¹, 黄枭坤¹, 曾仁芬¹, 陈超¹, 聂鑫¹, 成昊²()

1. 景德镇陶瓷大学材料科学与工程学院, 江西省先进陶瓷材料重点实验室, 景德镇 333001
2. 铜仁学院材料与化学工程学院, 铜仁 554300

收稿日期:2021-06-28 修回日期:2021-07-20 出版日期:2022-05-20 网络出版日期:2021-10-21
通讯作者: 江向平, 教授. E-mail: jiangxp64@163.com;成昊, 教授. E-mail:smallone.1@163.com
作者简介:叶芬(1987-), 女, 博士研究生. E-mail: yefen1987@163.com
基金资助:
国家自然科学基金(52062018);国家自然科学基金(51862016);国家自然科学基金(51762024);江西省自然科学基金(20192BAB20600);江西省自然科学基金(20192BAB212002);江西省教育厅科技项目(GJJ190712);江西省教育厅科技项目(GJJ190699);贵州省教育厅创新团队(KY[2018]030)

Dielectric and Energy Storage Property of (0.96NaNbO₃-0.04CaZrO₃)-xFe₂O₃ Antiferroelectric Ceramics

YE Fen¹^,²(), JIANG Xiangping¹(), CHEN Yunjing¹, HUANG Xiaokun¹, ZENG Renfen¹, CHEN Chao¹, NIE Xin¹, CHENG Hao²()

1. Jiangxi Key Laboratory of Advanced Ceramic Materials, School of Material Science and Engineering, Jingdezhen Ceramic Institute, Jingdezhen 333001, China
2. College of Material and Chemical Engineering, Tongren University, Tongren 554300, China

Received:2021-06-28 Revised:2021-07-20 Published:2022-05-20 Online:2021-10-21
Contact: JIANG Xiangping, professor. E-mail: jiangxp64@163.com; CHENG Hao, professor. E-mail: smallone.1@163.com
About author:YE Fen (1987-), female, PhD candidate. E-mail: yefen1987@163.com
Supported by:
National Natural Science Foundation of China(52062018);National Natural Science Foundation of China(51862016);National Natural Science Foundation of China(51762024);Natural Science Foundation of Jiangxi Province(20192BAB20600);Natural Science Foundation of Jiangxi Province(20192BAB212002);Foundation of Jiangxi Provincial Education Department(GJJ190712);Foundation of Jiangxi Provincial Education Department(GJJ190699);Foundation of the Department of Education of Guizhou province(KY[2018]030)

摘要/Abstract

摘要：

0.96NaNbO₃-0.04CaZrO₃(简称NNCZ)陶瓷在室温下展现出稳定的双电滞回线, 但是其储能密度、储能效率和击穿强度都比较低, 限制其成为储能材料。本工作通过掺杂Fe₂O₃, 利用Fe ³⁺离子变价的特点, 实现NNCZ储能性能的优化。采用传统固相法制备了(0.96NaNbO₃-0.04CaZrO₃)-xFe₂O₃(简称NNCZ-xFe)反铁电储能陶瓷, 并对样品的相结构、微观形貌、电学性能和储能性能进行了表征, 重点研究了Fe₂O₃掺杂量对NNCZ陶瓷介电和储能性能的影响规律。结果表明, 样品均具有单一的钙钛矿结构, 掺杂Fe₂O₃能明显降低NNCZ陶瓷的烧结温度, 晶粒平均尺寸随着掺杂量增大先减小后增大, 掺杂量x=0.02时, 晶粒平均尺寸最小(5.04 mm), 且具有较好的储能性能。室温下, NNCZ-0.02Fe击穿强度为230 kV/cm, 击穿前的有效储能密度和储能效率分别为1.57 J/cm ³和55.74%。在125 ℃和外加电场为180 kV/cm下, NNCZ-0.02Fe的储能密度为4.53 J/cm ³。掺杂Fe₂O₃使NNCZ陶瓷的烧成温度降低, 氧空位的迁移速率下降, 抑制晶粒的长大, 同时降低了介电损耗, 使得击穿强度增加; 适量氧空位钉扎使得反铁电相向铁电相相翻转变得困难, 避免出现哑铃状双电滞回线, 从而提高储能效率。本研究结果表明NNCZ-xFe在电介质储能领域具有潜在应用价值。

关键词: NaNbO₃, 反铁电, 储能性能, 介电性能

Abstract:

0.96NaNbO₃-0.04CaZrO₃(NNCZ) ceramic shows stable double hysteresis loops at room temperature, but the property of energy density, energy storage efficiency and breakdown strength of NNCZ are terrible, which limit NNCZ to be used as energy storage materials. In this work, Fe₂O₃ was chosen to modify the energy storage property of NNCZ. (0.96NaNbO₃-0.04CaZrO₃)-xFe₂O₃(NNCZ-xFe) antiferroelectric ceramics were prepared by traditional solid reaction method. The phase, morphology, dielectric property and energy storage property of NNCZ-xFe were characterized. The results indicated that the crystal structures of NNCZ-xFe ceramics were pure perovskite structure. The sintering temperature of NNCZ ceramic was decreased with addition of Fe₂O₃. With the increase of Fe₂O₃ content, the grain size of NNCZ-xFe were decreased firstly and then raised. The NNCZ-0.02Fe ceramic obtained the smallest grain size (5.04 μm) and the best energy storage property. The breakdown strength of NNCZ-0.02Fe was 230 kV/cm at room temperature (RT). The recoverable energy density and energy storage efficiency before breakdown were 1.57 J/cm ³and 55.74% respectively. At 125 ℃ and 180 kV/cm, the energy density of NNCZ- 0.02Fe was 4.53 J/cm ³. Fe₂O₃ doping decreased the sintering temperature of NNCZ ceramics, reduced the the migration rate of oxygen vacancies and inhibited the growth of grains. At the same time, it reduced the dielectric loss and improved the breakdown strength. The oxygen vacancies pinning made antiferroelectric phase switch to ferroelectric phase harder, avoided appearance dumbbell-shaped double hysteresis loops, so the energy storage efficiency was improved. This research shows that NNCZ-xFe has a good potential application in the field of dielectric energy storage.

Key words: NaNbO₃, antiferroelectric, energy storage property, dielectric property

中图分类号:

TQ174

叶芬, 江向平, 陈云婧, 黄枭坤, 曾仁芬, 陈超, 聂鑫, 成昊. (0.96NaNbO₃-0.04CaZrO₃)-xFe₂O₃反铁电陶瓷的介电及储能性能研究[J]. 无机材料学报, 2022, 37(5): 499-506.

YE Fen, JIANG Xiangping, CHEN Yunjing, HUANG Xiaokun, ZENG Renfen, CHEN Chao, NIE Xin, CHENG Hao. Dielectric and Energy Storage Property of (0.96NaNbO₃-0.04CaZrO₃)-xFe₂O₃ Antiferroelectric Ceramics[J]. Journal of Inorganic Materials, 2022, 37(5): 499-506.

图/表 8

图1 NNCZ-xFe陶瓷的XRD图谱 (a), 22.5º~22.8º放大图谱(b)和31.8º~33.0º放大图谱(c)

Fig. 1 XRD patterns of NNCZ-xFe ceramics (a), enlarged XRD patterns from 22.5° to 22.8° (b), and from 31.8° to 33.0° (c) of NNCZ-xFe ceramics

图2 NNCZ-xFe陶瓷的表面形貌照片及其平均粒径

Fig. 2 Surface morphologies of NNCZ-xFe ceramics and corresponding average grain size (a) x=0; (b) x=0.02; (c) Average grain size

图3 NNCZ-xFe陶瓷的O1s XPS图谱

Fig. 3 XPS spectra of O1s peak for NNCZ-xFe (a) x=0; (b) x=0.02

图4 NNCZ-xFe陶瓷的电阻率(ρ)随温度的变化曲线

Fig. 4 Temperature dependence of electrical resistivity (ρ) for NNCZ-xFe in the different temperature range

图5 NNCZ-xFe陶瓷的介电性能

Fig. 5 Dielectric property of NNCZ-xFe ceramics (a) Temperature dependence of relative permittivity of NNCZ-xFe ceramics; (b) Loss tangent of NNCZ-xFe ceramics; (c) Change of Curie temperature (TC) and dielectric constant at room temperature (RT) with the content of Fe3+colorful figures are available on website

图6 NNCZ-xFe陶瓷室温下测得的电滞回线

Fig. 6 P-E loops of NNCZ-xFe ceramics at room temperature (a) x=0; (b) x=0.005; (c) x=0.01; (d) x=0.015; (e) x=0.02; (f) x=0.025

图7 NNCZ-xFe陶瓷的击穿强度和储能性能

Fig. 7 Breakdown strength and energy storage property of NNCZ-xFe ceramics (a) Breakdown strength; (b) Energy storage property before breakdown; (c, d) Energy storage property at different electric fields

图8 NNCZ-0.02Fe陶瓷在不同温度和频率下的电滞回线储能性能

Fig. 8 P-E loops and energy storage properties of NNCZ-0.02Fe ceramics at different temperatures and different frequencies (a) P-E loops of different temperatures; (b) Energy storage properties of different temperatures; (c) P-E loops of different frequencies; (b) Energy storage properties of different frequency

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(0.96NaNbO₃-0.04CaZrO₃)-xFe₂O₃反铁电陶瓷的介电及储能性能研究

Dielectric and Energy Storage Property of (0.96NaNbO₃-0.04CaZrO₃)-xFe₂O₃ Antiferroelectric Ceramics

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