具有优异储能性能与充放电特性的类线性NaNbO3基无铅弛豫反铁电陶瓷

doi:10.15541/jim20230486

无机材料学报 ›› 2024, Vol. 39 ›› Issue (4): 423-431.DOI: 10.15541/jim20230486 CSTR: 32189.14.10.15541/jim20230486

所属专题：【信息功能】介电、铁电、压电材料（202409）

具有优异储能性能与充放电特性的类线性NaNbO₃基无铅弛豫反铁电陶瓷

石睿健(), 雷俊伟, 张祎, 谢爱文(), 左如忠()

安徽工程大学材料科学与工程学院, 先进陶瓷研究中心, 芜湖 241000

收稿日期:2023-10-20 修回日期:2023-12-10 出版日期:2024-04-20 网络出版日期:2024-01-08
通讯作者: 谢爱文, 讲师. E-mail: xieaiwen@ahpu.edu.cn;
左如忠, 教授. E-mail: zuoruzhong@ahpu.edu.cn
作者简介:石睿健(1998-), 男, 硕士研究生. E-mail: 1092348993@qq.com
基金资助:
国家重点研发计划(2022YFB3807403);安徽省高校创新团队项目(2022AH010058);国家自然科学基金(52302131);安徽省自然科学基金(2308085QE140)

Linear-like NaNbO₃-based Lead-free Relaxor Antiferroelectric Ceramics with Excellent Energy-storage and Charge-discharge Properties

SHI Ruijian(), LEI Junwei, ZHANG Yi, XIE Aiwen(), ZUO Ruzhong()

Center for Advanced Ceramics, School of Materials Science and Engineering, Anhui Polytechnic University, Wuhu 241000, China

Received:2023-10-20 Revised:2023-12-10 Published:2024-04-20 Online:2024-01-08
About author:SHI Ruijian (1998-), male, Master candidate. E-mail: 1092348993@qq.com
Supported by:
National Key R&D Program of China(2022YFB3807403);Innovation Team Project in Universities and Colleges(2022AH010058);National Natural Science Foundation of China(52302131);Natural Science Foundation of Anhui Province(2308085QE140)

摘要/Abstract

摘要：

反铁电材料由于电场诱导的反铁电-铁电相变而在高性能介质储能电容器应用中显示出极大的潜力。然而, 场致相变带来大的极化滞后使得反铁电材料难以同时获得高储能密度(W_rec)和高储能效率(η)。本工作通过在0.76NaNbO₃-0.24(Bi_0.5Na_0.5)TiO₃中引入第三组元Bi(Mg_0.5Ti_0.5)O₃调控其弛豫特性, 改善了NaNbO₃基无铅反铁电陶瓷的储能性能。采用传统固相合成法制备了(0.76-x)NaNbO₃-0.24(Bi_0.5Na_0.5)TiO₃-xBi(Mg_0.5Ti_0.5)O₃无铅弛豫反铁电陶瓷材料, 并研究了该材料的相结构、微观形貌以及介电、储能和充放电特性。结果表明, 引入Bi(Mg_0.5Ti_0.5)O₃在不改变基体反铁电正交R相结构的基础上明显增强了陶瓷的介电弛豫特性, 显著减小了陶瓷的极化滞后性。特别是在x=0.050组成中实现了具有极低滞后的类线性电滞回线。同时, 陶瓷的显微形貌还得到明显改善, 介电常数降低, 击穿场强显著提高。因此, x=0.050的组成在30 kV/mm的中等电场下同时获得了高的储能密度W_rec=3.5 J/cm³与储能效率η=93%。此外, x=0.050组成还显示出优异的充放电特性, 在20 kV/mm下具有高功率密度P_D=131(1±1%) MW/cm³、高放电能量密度W_D=1.66(1±6%) J/cm³以及快的放电速率t_0.9<290 ns。该充放电特性在25~125 ℃的宽温区内保持良好的稳定性。这些研究结果表明, 0.71NaNbO₃-0.24(Bi_0.5Na_0.5)TiO₃-0.050Bi(Mg_0.5Ti_0.5)O₃陶瓷是一种非常有应用潜力的高功率储能电容器介质材料。

关键词: 无铅陶瓷, 反铁电, 介电弛豫, 储能性能, 充放电特性

Abstract:

Antiferroelectric (AFE) materials exhibit great potential in the application of high-performance dielectric energy storage capacitors due to their electric field-induced AFE-ferroelectric (FE) phase transition. However, the large hysteresis of field-induced phase transition makes it difficult to simultaneously achieve high energy-storage density (W_rec) and efficiency (η) for AFEs. This work improved the energy-storage performance of NaNbO₃-based lead-free AFE ceramics by introducing the third group Bi(Mg_0.5Ti_0.5)O₃ into 0.76NaNbO₃-0.24(Bi_0.5Na_0.5) TiO₃ to regulate its relaxation characteristics. Novel lead-free AFE ceramics, (0.76-x)NaNbO₃-0.24(Bi_0.5Na_0.5)TiO₃-xBi(Mg_0.5Ti_0.5)O₃, were prepared by a traditional solid-state reaction method. Their phase structure and microstructure as well as dielectric, energy-storage, and charge-discharge characteristics were studied. The results indicated that introduction of Bi(Mg_0.5Ti_0.5)O₃ obviously enhanced the dielectric relaxor behavior of the matrix without changing its AFE R-phase structure, which led to the significantly reduced polarization hysteresis. Especially, a linear-like polarization-field hysteresis loop with extremely-low hysteresis was obtained in the composition of x=0.050. At the same time, microstructure of the ceramic was effectively optimized, its dielectric constant decreased, and its breakdown strength had significant enhanced. As a result, a high W_rec=3.5 J/cm³ and a high η=93% were simultaneously achieved under a moderate electric field of 30 kV/mm in the x=0.050 ceramic. Moreover, the x=0.050 ceramic also exhibited excellent charge-discharge characteristics with a high-power density P_D=131(1±1%) MW/cm³, a high discharge energy density W_D=1.66(1±6%) J/cm³ and a fast discharge rate t_0.9<290 ns at 20 kV/mm. The charge-discharge properties maintained good stability within a wide temperature range of 25-125 ℃. These results indicate that 0.71NaNbO₃-0.24(Bi_0.5Na_0.5)TiO₃-0.050Bi(Mg_0.5Ti_0.5)O₃ ceramics can be expected to be applied in high-power energy-storage capacitors.

Key words: lead-free ceramic, antiferroelectric, relaxor behavior, energy-storage property, charge-discharge characteristic

中图分类号:

TQ174

石睿健, 雷俊伟, 张祎, 谢爱文, 左如忠. 具有优异储能性能与充放电特性的类线性NaNbO₃基无铅弛豫反铁电陶瓷[J]. 无机材料学报, 2024, 39(4): 423-431.

SHI Ruijian, LEI Junwei, ZHANG Yi, XIE Aiwen, ZUO Ruzhong. Linear-like NaNbO₃-based Lead-free Relaxor Antiferroelectric Ceramics with Excellent Energy-storage and Charge-discharge Properties[J]. Journal of Inorganic Materials, 2024, 39(4): 423-431.

图/表 10

图1 不同组分(0.76-x)NN-0.24BNT-xBMT陶瓷的室温 XRD图谱

Fig. 1 XRD patterns of (0.76-x)NN-0.24BNT-xBMT ceramics with different composition at room temperature

图2 不同组分(0.76-x)NN-0.24BNT-xBMT陶瓷的全谱XRD结构精修

Fig. 2 Rietveld refinement results of XRD patterns for (0.76-x)NN-0.24BNT-xBMT ceramics with different compositions (a) x=0; (b) x=0.025; (c) x=0.050; (d) x=0.075

表1 全谱拟合的(0.76-x)NN-0.24BNT-xBMT陶瓷精修结果参数

Table 1 Refined structural parameters of full spectrum fitting for (0.76-x)NN-0.24BNT-xBMT ceramics

x	Space group	Lattice parameters	V/nm³	R_wp/%	R_p/%	χ²
0	Pnma	a=0.77920 nm, b=0.77852 nm, c=2.33854 nm, α=β=γ=90^o	1.418608	5.35	3.70	3.62
0.025	Pnma	a=0.77965 nm, b=0.77897 nm, c=2.34045 nm, α=β=γ=90^o	1.421413	5.20	3.62	3.59
0.050	Pnma	a=0.77899 nm, b=0.77995 nm, c=2.33913 nm, α=β=γ=90^o	1.421193	6.27	4.05	4.17
0.075	Pnma	a=0.78060 nm, b=0.78000 nm, c=2.34481 nm, α=β=γ=90^o	1.427666	4.99	3.56	2.96

图3 (0.76-x)NN-0.24BNT-xBMT陶瓷的晶格常数比随组成的变化

Fig. 3 Evolution of lattice constant ratios for (0.76-x)NN-0.24BNT-xBMT ceramics with composition

图4 (0.76-x)NN-0.24BNT-xBMT陶瓷样品热腐蚀表面的晶粒形貌及相应晶粒分布图

Fig. 4 Grains morphologies of thermally etched surfaces of (0.76-x)NN-0.24BNT-xBMT ceramics and corresponding grain distributions

图5 (0.76-x)NN-0.24BNT-xBMT陶瓷的介电常数和介电损耗随温度的变化曲线

Fig. 5 Temperature dependent curves of εr and tanδ of (0.76-x)NN- 0.24BNT-xBMT ceramics

图6 (0.76-x)NN-0.24BNT-xBMT陶瓷耐击穿性能的威布尔分布图(a)以及EB随组成的变化(b)

Fig. 6 Weibull distributions of (0.76-x)NN-0.24BNT-xBMT ceramics breakdown resistance (a) and variation of EB with composition (b)

图7 (0.76-x)NN-0.24BNT-xBMT陶瓷的储能性能

Fig. 7 Energy-storage properties of (0.76-x)NN-0.24BNT-xBMT ceramics (a, b) P-E hysteresis loops (a) and energy-storage performance (b) of different compositions measured at 20 kV/mm; (c, d) P-E hysteresis loops (c) and energy-storage performance (d) of the x=0.050 ceramic measured under different electric fields

图8 (0.76-x)NN-0.24BNT-xBMT(x=0.050)陶瓷的变电场充放电特性

Fig. 8 Electric field-dependent charge-discharge characteristics of (0.76-x)NN-0.24BNT-xBMT (x=0.050) ceramics (a, b) Overdamped discharging current curves (a) and WD versus time curves (b) of the x=0.050 ceramic under different electric fields; (c, d) Underdamped discharging curves (c) and variation of PD, WD, and t0.9 (d) of the x=0.050 ceramics

图9 (0.76-x)NN-0.24BNT-xBMT(x=0.050)陶瓷的变温充放电特性

Fig. 9 Temperature-dependent charge-discharge characteristics of (0.76-x)NN-0.24BNT-xBMT (x=0.050) ceramics (a, b) Overdamped discharging current curves (a) and WD versus time curves (b) of the x=0.050 ceramic under different electric fields; (c, d) Underdamped discharging curves (c) and variation of PD, WD, and t0.9 (d) of the x=0.050 ceramics

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具有优异储能性能与充放电特性的类线性NaNbO₃基无铅弛豫反铁电陶瓷

Linear-like NaNbO₃-based Lead-free Relaxor Antiferroelectric Ceramics with Excellent Energy-storage and Charge-discharge Properties

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