硅酸盐学报

稀土掺杂对铌酸钠基陶瓷介电及储能性能的影响

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王传民 ¹ , 张海波 ¹^,³ , 郭新 ¹^,³ , 肖建中 ¹^,³ , 张晓东 ¹^,³ , 张顺平 ¹^,³ , 谢兵 ² , 谭划 ¹^,³

硅酸盐学报 | 电介质储能材料专刊—研究论文 2024,52(4): 1240-1249

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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) : 1240 -1249

稀土掺杂对铌酸钠基陶瓷介电及储能性能的影响

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王传民¹, 张海波¹^,³, 郭新¹^,³, 肖建中¹^,³, 张晓东¹^,³, 张顺平¹^,³, 谢兵², 谭划¹^,³

作者信息

^1．华中科技大学材料科学与工程学院，材料成形与模具技术国家重点实验室武汉 430074

^2．南昌航空大学材料科学与工程学院南昌 330063

^3．广东华中科技大学工业技术研究院广东东莞 523808

通讯作者:

谭划（1990—），男，博士，助理研究员。

谢兵（1983—），男，博士，副教授。

作者简介:

王传民（2001—），男，硕士研究生。

Effect of Rare-Earth Doping on Dielectric and Energy Storage Performance of Sodium Niobate-Based Ceramics

Chuanmin WANG¹, Haibo ZHANG¹^,³, Xin GUO¹^,³, Jianzhong XIAO¹^,³, Xiaodong ZHANG¹^,³, Shunping ZHANG¹^,³, Bing XIE², Hua TAN¹^,³

Affiliations

^1.State Key Laboratory of Materials Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, China

^2.School of Materials Science and Engineering, Nanchang Hangkong University, Nanchang, 330063, China

^3.Guangdong HUST Industrial Technology Research Institute, Dongguan 523808, Guangdong, China

Corresponding Author:

TAN Hua (1990-), male, Ph.D., Research Associate. E-mail: hua_tan@hust.edu.cn;

XIE Bing (1983-), male, Ph.D., Associate Professor. xieb@nchu.edu.cn

WANG Chuanmin (2001-), male, Master candidate. E-mail: 1967817852@qq.com

出版时间: 2024-04-20 doi: 10.14062/j.issn.0454-5648.20230669

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摘要

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随着对电子器件高度集成化、小型化的需求，电介质陶瓷逐渐成为脉冲电力电子系统中关键材料之一。其中，具有大的最大极化、小的剩余极化以及低的介电损耗的反铁电储能陶瓷逐渐成为最佳的储能陶瓷材料。采用固相反应法制备了Sm³⁺掺杂的0.9NaNbO₃-0.1BiFeO₃（NN-BF）基弛豫反铁电陶瓷，化学式为（1-x）［0.9NaNbO₃-0.1BiFeO₃］-xSm₂O₃（x=0.01，0.02，0.03，0.04），系统地探究了Sm³⁺掺杂对NN-BF基储能陶瓷物相结构、微观形貌、介电性能及储能性能的影响。结果表明：随着Sm³⁺掺杂量的增加，储能陶瓷的晶粒尺寸和剩余极化均呈现先减小后增大的趋势，而击穿场强、最大极化、储能密度及储能效率均呈现先增大后减小的趋势。此外，由于Sm元素价态不稳定，适量掺杂Sm³⁺可以稳定Fe³⁺的价态，使NN-BF的反铁电相更加稳定。当Sm³⁺的掺杂量为x=0.02时，NN-BF陶瓷反铁电相的稳定性以及铁电相的弛豫性均得到了增强，此时击穿场强达到438 KV/cm，室温下储能密度及储能效率分别为3.67 J/cm³及71.63%，呈现较好的储能性能。

关键词

稀土掺杂 / 反铁电陶瓷 / 击穿场强 / 储能密度

Abstract

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Introduction

The common energy storage devices mainly include supercapacitors, lithium-ion batteries, fuel cells, and ceramic capacitors. Compared to other energy storage devices, ceramic capacitors have attracted much attention due to their ultra-high charge-discharge rates and power density. Antiferroelectric ceramics exhibit a large maximum polarization and close-to-zero residual polarization, displaying characteristics of a double hysteresis loop. Also, antiferroelectric ceramics have an advantage of low dielectric loss, making them one of the optimal energy storage materials. Lead-free NaNbO₃-based antiferroelectric ceramics become popular due to the environmental concern and cost reduction. However, NaNbO₃-based ceramics can transform from an antiferroelectric phase to a ferroelectric phase at a certain applied electric field. Even after removing the applied electric field, some ferroelectric phase remains, increasing the residual polarization strength and affecting the formation of the double hysteresis loop at room temperature. Furthermore, a transition between antiferroelectric phase and ferroelectric phase caused by the complex phase structure results in a loss of most energy in the form of heat, reducing the energy storage efficiency (η). To further regulate the energy storage characteristics of NN-based antiferroelectric ceramics, this paper introduced Bi³⁺ and Fe³⁺ into the NaNbO₃ matrix to enhance the stability of the antiferroelectric phase and the relaxor behavior of the ferroelectric phase, resulting in a relaxor antiferroelectric ceramic. Different molar fractions of Sm₂O₃ were doped into the NN-BF ceramics with Sm³⁺ solid solution into the NaNbO₃ lattice. In addition, the influence of doping amount of Sm³⁺ on the phase structure, microstructure, dielectric properties, and energy storage performance of NN-BF ceramics was also investigated.

Methods

Different Sm³⁺ doping amounts of (1-x)[0.9NaNbO₃-0.1BiFeO₃]-xSm₂O₃ (x=0.01, 0.02, 0.03, 0.04) relaxor antiferroelectric ceramics were prepared via conventional solid-state reaction. The ceramic green bodies with a diameter of 10 mm and a thickness of 1 mm were prepared. They were sintered in a furnace at a rate of 3 ℃/min at 1,150 ℃ for 3 h, and then cooled naturally to form ceramics. The ceramic samples were polished to a thickness of 0.1 mm, and silver electrodes with a radius of 2 mm were screen-printed on the upper and lower surfaces of the ceramic samples. The samples were heated at 500 ℃ for 1 h to connect the ceramics and electrodes tightly. The phase structures of different ceramic samples were analyzed by an X-ray diffractometer. The microstructure and elemental distribution of the ceramic samples were analyzed by a field emission scanning electron microscope. The dielectric loss and dielectric constant of the ceramic samples at different temperatures (i.e., 25~300 ℃) and frequencies (i.e., 1, 10, 100, 500, 1 000 kHz) were tested by an LCR meter. The electric hysteresis loops of the ceramic samples were measured at room temperature and 10 Hz by a ferroelectric tester, and the energy density and energy storage efficiency of the ceramic samples were calculated based on these measurements. The XPS spectra of Fe 2p in ceramic samples with different Sm³⁺ doping amounts (x=0.01, 0.02, and 0.03) were determined by an X-ray photoelectron spectrometer.

Results and discussion

The XRD patterns show that the ceramic with the Sm³⁺ doping amount (x) of 0.01 or 0.02 has a homogeneous perovskite structure without the second phase. Bi³⁺, Fe³⁺, and Sm³⁺ are all solid-solutions into the NaNbO₃ lattice. When the Sm³⁺ doping amount (x) is 0.02, Sm³⁺ occupies the position of Na⁺ in the NaNbO₃ lattice. The lattice energy increases after solid solution since the ionic radius of Sm³⁺ is greater than that of Na⁺, inhibiting the growth of grains. Consequently, the microstructure of the ceramic becomes denser, with smaller and more uniformly distributed grains. The larger dielectric constant reduces the breakdown field strength of the ceramic, while the smaller dielectric constant decreases the polarization of the ceramic. Therefore, a moderate dielectric constant is conducive to achieving a larger energy storage density for the ceramic composition when the Sm³⁺ doping amount (x) is 0.02. The hysteresis loop of the NN-BF ceramic is relatively slender, resembling a "waist-like" shape typical of relaxor antiferroelectric. This is because the doping of Bi³⁺ and Fe³⁺ enhances the stability of the antiferroelectric phase and the relaxor behavior of the ferroelectric phase. The XPS spectra of Fe 2p indicate that an appropriate doping of Sm³⁺ can stabilize the valence state of Fe³⁺, further stabilizing the antiferroelectric phase of NN-BF and reducing the generation of oxygen vacancies in the ceramic. This leads to an increase in the breakdown field strength.

Bi³⁺ in the A-site of the 0.9NaNbO₃-0.1BiFeO₃ lattice is gradually replaced by Sm³⁺, resulting in the appearance of the second phase Bi₂O₃. The low-melting-point Bi₂O₃ plays a role in promoting sintering during the firing process, thereby facilitating the grain growth. However, the second phase Bi₂O₃ is not resistant to breakdown, leading to a decrease in the breakdown field strength of the ceramic.

Conclusions

The stability of the antiferroelectric phase and the relaxor behavior of the ferroelectric phase in NN-BF ceramics with the Sm³⁺ doping amount of 0.02 were enhanced. An appropriate doping of Sm³⁺ could stabilize the valence state of Fe³⁺, further stabilizing the antiferroelectric phase of NN-BF ceramics. In an applied electric field of 300 kV/cm, the maximum polarization (P_max) of NN-BF ceramics (i.e., 17.83 μC/cm²), the minimum residual polarization (P_r) (i.e., 2.87 μC/cm²), and the maximized P_max-P_r (i.e., 14.96 μC/cm²) were obtained. The energy density and energy storage efficiency of NN-BF ceramics both reached their maximum values (i.e., 3.67 J/cm³ and 71.63%), respectively. The breakdown field strength of the ceramic was calculated to be 438 kV/cm through the Weibull distribution. These results indicated that NN-BF relaxor antiferroelectric ceramics with an appropriate Sm³⁺ doping could have promising potential applications in energy storage.

Key words

rare earth doping / antiferroelectric ceramics / breakdown field strength / energy storage density

引用本文

王传民, 张海波, 郭新, 肖建中, 张晓东, 张顺平, 谢兵, 谭划. 稀土掺杂对铌酸钠基陶瓷介电及储能性能的影响. 硅酸盐学报, 2024 , 52 (4) : 1240 -1249 . DOI: 10.14062/j.issn.0454-5648.20230669

Chuanmin WANG, Haibo ZHANG, Xin GUO, Jianzhong XIAO, Xiaodong ZHANG, Shunping ZHANG, Bing XIE, Hua TAN. Effect of Rare-Earth Doping on Dielectric and Energy Storage Performance of Sodium Niobate-Based Ceramics[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (4) : 1240 -1249 . DOI: 10.14062/j.issn.0454-5648.20230669

基金

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国家自然科学基金青年科学基金(52202133)
广东省基础与应用基础研究基金(2023A1515010373)
光谷实验室创新项目(OVL2023ZD001)
东莞市引进创新科研团队计划(202060 7101007)
国家自然科学基金面上项目(52372109)

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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.0454-5648.20230669

接收时间：2023-08-31
首发时间：2026-10-22
出版时间：2024-04-20

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收稿日期：2023-08-31
修回日期：2023-09-28

基金

国家自然科学基金青年科学基金(52202133)

广东省基础与应用基础研究基金(2023A1515010373)

光谷实验室创新项目(OVL2023ZD001)

东莞市引进创新科研团队计划(202060 7101007)

国家自然科学基金面上项目(52372109)

作者信息

^1．华中科技大学材料科学与工程学院，材料成形与模具技术国家重点实验室武汉 430074

^2．南昌航空大学材料科学与工程学院南昌 330063

^3．广东华中科技大学工业技术研究院广东东莞 523808

通讯作者:

谭划（1990—），男，博士，助理研究员。

谢兵（1983—），男，博士，副教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20230669

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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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