硅酸盐学报

铌酸钠基无铅陶瓷的弛豫反铁电相构筑与储能特性优化

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杨伟伟 ¹^,² , 曾华荣 ¹^,² , 翟继卫 ³ , 赵坤宇 ¹^,² , 李国荣 ¹^,²

硅酸盐学报 | 电介质储能材料专刊—研究论文 2024,52(4): 1200-1210

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硅酸盐学报 |电介质储能材料专刊—研究论文 2024 , 52 (4) : 1200 -1210

铌酸钠基无铅陶瓷的弛豫反铁电相构筑与储能特性优化

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杨伟伟¹^,², 曾华荣¹^,², 翟继卫³, 赵坤宇¹^,², 李国荣¹^,²

作者信息

^1．中国科学院上海硅酸盐研究所，上海 201899

^2．中国科学院大学材料科学与光电技术学院，北京 100049

^3．同济大学材料科学与工程学院，上海 201804

通讯作者:

曾华荣（1972—），男，博士，研究员；

翟继卫（1963—），男，博士，教授。

作者简介:

杨伟伟（1989—），女，博士后。

Relaxor Antiferroelectric Phase and Optimized Energy Storage Properties of NaNbO₃-Based Lead-Free Ceramics

Weiwei YANG¹^,², Huarong ZENG¹^,², Jiwei ZHAI³, Kunyu ZHAO¹^,², Guorong LI¹^,²

Affiliations

^1.Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 201899, China

^2.College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing 100049, China

^3.School of Materials Science and Engineering, Tongji University, Shanghai 201804, China

Corresponding Author:

ZENG Huarong (1972-), male, Ph.D., Professor. E-mail: huarongzeng@mail.sic.ac.cn;

ZHAI Jiwei (1963-), male, Ph.D., Professor. apzhai@tongji.edu.cn

YANG Weiwei (1989-), female, Postdoctor. E-mail: yangweiwei@mail.sic.ac.cn

出版时间: 2024-04-20 doi: 10.14062/j.issn.0454-5648.20230734

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摘要

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开发具有优异综合储能特性的无铅陶瓷电容器是脉冲功率技术领域的迫切需求。相较于其他无铅储能陶瓷体系，NaNbO₃（NN）陶瓷具有结构相变丰富、理论密度低、电学可调性强、轻量化发展潜力大等显著优点，因而备受关注，成为当前的研究热点。基于降低容忍因子稳定反铁电相和增强陶瓷弛豫性的策略，开展了NN基弛豫反铁电陶瓷的制备与储能特性研究。通过引入BiFeO₃和Sr（Ti_0.85Zr_0.15）O₃成功制备了0.9［0.9NaNbO₃-0.1BiFeO₃］-0.1Sr（Ti_0.85Zr_0.15）O₃陶瓷，相较于纯NN陶瓷（0.14 J/cm³、6.39%）和0.9NaNbO₃-0.1BiFeO₃陶瓷（3.55 J/cm³和70.61%），其储能特性显著提升，储能密度（W_rec）与储能效率（η）分别达到了5.22 J/cm³、83.92%。其优异的储能特性源于BiFeO₃和Sr（Ti_0.85Zr_0.15）O₃掺杂对陶瓷的晶粒细化、反铁电相稳定性和弛豫特性的双增强机制。同时，0.9［0.9NaNbO₃-0.1BiFeO₃］-0.1Sr（Ti_0.85Zr_0.15）O₃陶瓷表现出良好的温度及频率稳定性，是一种极具应用前景的电介质储能材料。

关键词

铌酸钠 / 无铅陶瓷 / 反铁电 / 储能特性 / 充放电特性

Abstract

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Introduction

Pulse power technology has important applications in national defense industry. Dielectric capacitor is one of the energy storage components of pulse power devices. Ceramic dielectric capacitors have some advantages like fast charging-discharging speed, good electromechanical performance, anti-aging, and resistance to extreme conditions, which can be used in dielectric energy storage. The existing energy storage properties of BaTiO₃-based dielectric ceramics are generally low at a high electric field, and lead-based ceramic capacitors are increasingly limited because of the presence of lead as a highly toxic element. It is thus necessary for pulse power technology to develop lead-free ceramic capacitors with superior comprehensive energy storage properties. NaNbO₃ (NN) ceramics have a rich structural phase transition and a low theoretical density, which makes their electrical properties highly adjustable and is conducive to the development of lightweight capacitors. Recent work on relaxor ferroelectric, anti-ferroelectric and relaxor antiferroelectric NaNbO₃-based ceramics are performed. Compared with the typical lead-free antiferroelectric AgNbO₃, NN as one of of lead-free antiferroelectric materials has some advantages like low theoretical density (i.e., 4.55 g/cm³), high polarization intensity (i.e., 40 μC/cm²), simple preparation process, and relatively low raw material cost. Developing NN-based relaxor antiferroelectric ceramics with superior comprehensive energy storage properties is still a challenge because of the contradiction between polarization and breakdown strength. Therefore, exploring a relationship between the structure and energy storage properties of NN-based relaxor antiferroelectric ceramics is still a research aspect for NN-based ceramics. In this paper, a strategy of reducing tolerance factor was adopted to stabilize the antiferroelectric phase of NN-based ceramics. 10% (in mole fraction) BiFeO₃(BF) with a low tolerance factor (i.e., 0.954 3) was incorporated into pure NN as a second end member, and the antiferroelectric R phase (Pbnm) of NN ceramics was stabilized at room temperature. The third end member Sr(Ti_0.85Zr_0.15)O₃(STZ) was introduced to further improve the relaxor characteristic of the ceramics, and then the relaxor antiferroelectric phase was constructed in NN-based ceramics. In addition, the phase structure, microstructure, energy storage properties, stability and charging-discharging performance of the ceramics were also analyzed.

Methods

The chemical composition of the ceramics was NaNbO₃, 0.9NaNbO₃-0.1BiFeO₃, and (1-x)[0.9 NaNbO₃-0.1BiFeO₃]-xSr(Ti_0.85Zr_0.15)O₃, where x=0.05, 0.10, 0.15. All the ceramics were prepared by a conventional solid phase method. The ceramics were prepared via sintering at 1 230-1 260 ℃ for 2 h. The crystal structure of ceramics was analyzed by a model DX-2700BH X-ray diffractometer (Haoyuan Instrument Co., China) and a model Lab-Ram HR800 spectrometer (HORIBA Co., France) with a laser wavelength of 532 nm. The in-situ temperature test for Raman spectra was performed on a model Linkam THMS600 temperature control platform. The sample used for in-situ electric field Raman spectroscopy test was plated with an electrode by an ion sputtering method. The sputtering current was set to 6 mA and the sputtering time to 2 min to ensure that the sample had both electrical conductivity and the penetration in Raman spectroscopic laser. The natural surface morphology of the samples was determined by a scanning electron microscope, and the grain size of the ceramics was determined using a software named Nano Measurer. After the sample was thinned, the domain structure of the ceramics was characterized by a model JEM-2100F field emission transmission electron microscope. The sample was polished to 0.5 mm thickness, cleaned, and coated with silver electrodes on the upper and lower surfaces of the sample. The dielectric properties of the ceramics were measured at -120 -450 ℃ by a model E4980A precision LCR bridge (Agilent Co., USA). The hysteresis loops of the ceramics with the thickness of 150 μm were tested by a model Precision Premier II ferroelectric tester (Radiant Co., USA).

Results and discussion

Based on the XRD patterns, NN, NN-BF and NN-BF-xSTZ ceramics are a pure perovskite structure. NN ceramics show diffraction peaks for phases (110) and (200), manifesting that they are antiferroelectric orthogonal P(Pbcm) phases at room temperature. The orthogonal phase features disappear, and the diffraction peaks of phases (110) and (200) change from split state to single peak with the addition of BF and STZ, indicating that the addition of BF and STZ improves the symmetry of the ceramic and the ceramic transforms into a pseudo-cubic phase. NN ceramics have a dielectric anomaly peak at 400 ℃, which represents a transition from the antiferroelectric P phase to the antiferroelectric R phase. For NN-BF and NN-BF-xSTZ ceramics, the P-R phase transition peak disappears, and a diffuse dielectric anomaly peak appears at -100 ℃. Compared with NN ceramics, the room temperature dielectric constant of NN-BF ceramics increases, which is mainly due to the presence of anti-ferroelectric R phase in the ceramics. The in-situ XRD and Raman measurements show that the symmetry of the local structure of NN-BF-10STZ ceramics has a good stability. After BF and STZ doping, the grain size of the ceramics is reduced and the grain distribution uniformity is improved. The breakdown strength of ceramics can be enhanced due to the effect of decreasing grain size and improving distribution uniformity. STZ doping reduces the size of antiferroelectric domains. They can respond quickly to an external electric field due to the high activity and low energy barrier of nano-domains, thus reducing the remanent polarization, which is conducive to improving the energy storage properties. The transformation from antiferroelectric phase to ferroelectric phase of NN ceramics only occurs in the presence of the electric field. After the introduction of BF, the antiferroelectric R phase of the ceramics is stabilized, and the P-E curve shows a double hysteresis loop. The relaxation characteristics of the ceramics are further enhanced with the introduction of STZ. The P-E loops of NN-BF-10STZ ceramics become more elongated, and the polarization hysteresis is suppressed. The NN-BF-10STZ achieves the optimal energy storage properties (i.e., W_rec of 5.22 J/cm³ and η of 83.92%). Also, NN-BF-10STZ ceramics have a superior stability at 25-120 ℃ and 10-150 Hz.

Conclusions

Pure NN ceramics exhibited a typical square hysteresis loop with low energy storage density and efficiency (i.e., W_rec of 0.14 J/cm³, and η of 6.69%). After the introduction of the second component of BF, the ceramics had a double hysteresis loop like antiferroelectric, and the energy storage characteristics (i.e., W_rec~3.55 J/cm³, η~70.61%) were optimized. Furthermore, the introduction of STZ enhanced the relaxation of the ceramics, and reduced the polarization hysteresis of the hysteresis loop. The energy storage properties were optimized (i.e., W_rec~5.22 J/cm³, η~83.92%). 0.9[0.9NaNbO₃-0.1BiFeO₃]-0.1Sr(Ti_0.85Zr_0.15)O₃ ceramics with the optimal energy storage performance had a stability at different temperatures and frequencies, which could be used as a promising dielectric energy storage material with application prospects.

Key words

sodium niobate / lead-free ceramics / antiferroelectric / energy storage properties / charging-discharging properties

引用本文

杨伟伟, 曾华荣, 翟继卫, 赵坤宇, 李国荣. 铌酸钠基无铅陶瓷的弛豫反铁电相构筑与储能特性优化. 硅酸盐学报, 2024 , 52 (4) : 1200 -1210 . DOI: 10.14062/j.issn.0454-5648.20230734

Weiwei YANG, Huarong ZENG, Jiwei ZHAI, Kunyu ZHAO, Guorong LI. Relaxor Antiferroelectric Phase and Optimized Energy Storage Properties of NaNbO₃-Based Lead-Free Ceramics[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (4) : 1200 -1210 . DOI: 10.14062/j.issn.0454-5648.20230734

基金

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国家重点研发计划(2021YFB3800604; 2021YFA0716502)
国家自然科学基金(51831010)
中国科学院上海分院“基础研究特区计划”项目(JCYJ-SHFY-2022-022)
上海市“超级博士后”激励计划
国家资助博士后研究人员计划

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2024年第52卷第4期

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文章信息

doi: 10.14062/j.issn.0454-5648.20230734

接收时间：2023-09-21
首发时间：2026-10-22
出版时间：2024-04-20

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出版历史

收稿日期：2023-09-21
修回日期：2023-10-18

基金

国家重点研发计划(2021YFB3800604; 2021YFA0716502)

国家自然科学基金(51831010)

中国科学院上海分院“基础研究特区计划”项目(JCYJ-SHFY-2022-022)

上海市“超级博士后”激励计划

国家资助博士后研究人员计划

作者信息

^1．中国科学院上海硅酸盐研究所，上海 201899

^2．中国科学院大学材料科学与光电技术学院，北京 100049

^3．同济大学材料科学与工程学院，上海 201804

通讯作者:

曾华荣（1972—），男，博士，研究员；

翟继卫（1963—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20230734

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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