(1-x)NaNbO3-x(0.3Bi0.5Na0.5TiO3-0.7BiFeO3)陶瓷的介电以及储能性能研究

doi:10.6023/A24010028

摘要/Abstract

采用常规固相法制备(1－x)NaNbO₃-x(0.3Bi_0.5Na_0.5TiO₃-0.7BiFeO₃) [NN-x(BNT-BF)] (x=0.05, 0.1, 0.15, 0.2)陶瓷, 并对其物相组成、微观形貌、介电与储能特性进行系统研究. 结果表明, 随着BNT-BF含量的增加, NN-x(BNT-BF)陶瓷逐渐由正交反铁电P相和R相共存(x<0.1)转变为单一反铁电R相(x≥0.1), 弛豫行为增强. BNT-BF掺杂显著改善了陶瓷的致密度, 且陶瓷的平均晶粒尺寸随着掺杂量增大先减小后增大. 同时取代NaNbO₃的A位和B位可破坏NN原有的铁电长程有序结构, 优化陶瓷的储能性能. 在410 kV/cm的击穿场强(E_b)下, NN-0.2(BNT-BF)陶瓷的有效储能密度(W_rec)和储能效率(η)分别为2.54 J/cm³和89.24%, 且在20~120 ℃的温度范围内具有高的温度稳定性. 同时, 高功率密度(P_D=49 MW/cm³)、大电流密度(C_D=406 A/cm²)和超快放电速度(t_0.9=35 ns)使得NN-0.2(BNT-BF)陶瓷在脉冲功率系统中具有潜在的应用前景.

关键词: 铌酸钠, 介电性能, 储能性能, 温度稳定性, 充放电性能

Sodium niobate (NaNbO₃) ceramic, as a representative of antiferroelectric materials, has been widely studied in the field of energy storage due to its environmental friendliness and non-toxicity. However, its application is greatly limited due to its square hysteresis loop, which leads to low recoverable energy storage density (W_rec). Introducing a second component into NaNbO₃ to form a solid solution can enhance its energy storage properties. According to this train of thoughts, (1－x)NaNbO₃-x(0.3Bi_0.5Na_0.5TiO₃-0.7BiFeO₃) [NN-x(BNT-BF)] (x=0.05, 0.1, 0.15, 0.2) ceramics were designed through substituting the A- and B- sites of NaNbO₃ with Bi³⁺, Fe³⁺, and Ti⁴⁺ simultaneously in this work. The NN-x(BNT-BF) ceramics were prepared by the conventional solid-state reaction method, and their phase compositions, microstructures, dielectric and energy storage properties were systematically investigated by X-ray diffraction (XRD), Raman spectrum, scanning electron microscopy (SEM), dielectric property measurement and ferroelectric test. The results showed that with the increase of BNT-BF content, the phase composition of the NN-x(BNT-BF) ceramics gradually transformed from coexistence of orthogonal antiferroelectric P and R phases (x<0.1) to single antiferroelectric R phase (x≥0.1), and the relaxation behavior was significantly enhanced. The densification of the NN-x(BNT-BF) ceramics was remarkably improved. With the increase of BNT-BF content, the average grain size of the NN-x(BNT-BF) ceramics was firstly declined and then increased. Moreover, replacing the A- and B- sites of NaNbO₃ by Bi³⁺, Fe³⁺, and Ti⁴⁺ simultaneously could disrupt its original long-range antiferroelectric ordered structure, thus optimizing energy storage performances of the ceramics. At a high breakdown field strength (E_b) of 410 kV/cm, the NN-0.2(BNT-BF) ceramic achieved W_rec of 2.54 J/cm³, and energy storage efficiency (η) of 89.24%. In addition, the NN-0.2(BNT-BF) ceramic exhibited a high temperature stability in the temperature range of 20~120 ℃. Meanwhile, large power density (P_D=49 MW/cm³), high current density (C_D=406 A/cm²), and ultrafast discharge rate (t_0.9=35 ns) made the NN-0.2(BNT-BF) ceramic have potential applications in pulse power systems.

Key words: sodium niobate, dielectric property, energy storage property, temperature stability, charge-discharge property

引用此文

郭云凤, 王俊贤, 王泽星, 李家茂, 刘畅. (1-x)NaNbO₃-x(0.3Bi_0.5Na_0.5TiO₃-0.7BiFeO₃)陶瓷的介电以及储能性能研究[J]. 化学学报, 2024, 82(5): 511-519.

Yunfeng Guo, Junxian Wang, Zexing Wang, Jiamao Li, Chang Liu. Dielectric and Energy Storage Properties of (1-x)NaNbO₃-x(0.3Bi_0.5Na_0.5TiO₃-0.7BiFeO₃) Ceramics[J]. Acta Chimica Sinica, 2024, 82(5): 511-519.

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图/表 14

图1. (a) NN-x(BNT-BF)陶瓷的XRD谱图; (b) (200)衍射峰在45.5°~47.5°的放大谱图

Figure 1. (a) XRD patterns of NN-x(BNT-BF) ceramics; (b) amplified XRD patterns of (200) peak at 45.5°~47.5°

图2. NN-x(BNT-BF)陶瓷的Rietveld精修结果: (a) x=0.05, (b) x=0.1, (c) x=0.15, (d) x=0.2

Figure 2. Rietveld refinement results of NN-x(BNT-BF) ceramics: (a) x=0.05, (b) x=0.1, (c) x=0.15, (d) x=0.2

x	Phase	Lattice parameter				V_m/nm³
x	Phase	a/nm	b/nm	c/nm	α=β=γ/(°)	V_m/nm³
0.05	Pbma	0.555(5)	1.559(5)	0.550(3)	90	0.47689(0)
0.05	Pnma	0.782(8)	0.781(2)	2.346(9)	90	1.43549(3)
0.1	Pnma	0.781(6)	0.781(6)	2.344(6)	90	1.43259(8)
0.15	Pnma	0.781(6)	0.782(4)	2.347(3)	90	1.43573(9)
0.2	Pnma	0.783(4)	0.783(4)	2.344(7)	90	1.43921(0)

表1. NN-x(BNT-BF)陶瓷的Rietveld结构精修参数

Table 1. Rietveld refined lattice parameters of NN-x(BNT-BF) ceramics

图3. (a) NN-x(BNT-BF)陶瓷的拉曼光谱; (b) x=0.05样品和(c) x=0.1样品的Gaussian-Lorentz拟合图谱

Figure 3. (a) Raman spectra of NN-x(BNT-BF) ceramics; Gaussian- Lorentz fitting spectra of the samples with (b) x=0.05 and (c) x=0.1

图4. NN-x(BNT-BF)陶瓷的表面形貌及其晶粒尺寸分布: (a) x=0.05, (b) x=0.1, (c) x=0.15, (d) x=0.2

Figure 4. Surface morphologies and grain size distributions of NN-x(BNT-BF) ceramics: (a) x=0.05, (b) x=0.1, (c) x=0.15, (d) x=0.2

图5. NN-0.2(BNT-BF)陶瓷的能量色散X射线光谱面扫描图

Figure 5. Energy dispersive X-ray spectrometer mapping images of NN-0.2(BNT-BF) ceramics

图6. NN-x(BNT-BF)陶瓷在不同频率下εr和tan δ随温度的变化: (a) x=0.05, (b) x=0.1, (c) x=0.15, (d) x=0.2; (e) 10 kHz下的εr的温度依赖性; (f) 10 kHz下NN-x(BNT-BF)陶瓷的?ε/ε150 ℃的温度依赖性

Figure 6. Variation of εr and tan δ of NN-x(BNT-BF) ceramics with temperature at different frequencies: (a) x=0.05, (b) x=0.1, (c) x=0.15, (d) x=0.2; (e) dependence of εr on temperature at 10 kHz; (f) dependence of ?ε/ε150 ℃ on temperature for NN-x(BNT-BF) ceramics at 10 kHz

图7. NN-x(BNT-BF)陶瓷的TEM图: (a) x=0.05, (b) x=0.2

Figure 7. TEM images of NN-x(BNT-BF) ceramics: (a) x=0.05, (b) x=0.2

图8. NN-x(BNT-BF)陶瓷εr和tan δ的频率依赖性: (a) x=0.05, (b) x=0.1, (c) x=0.15, (d) x=0.2

Figure 8. Dependences of εr and tan δ on frequency for NN-x(BNT-BF) ceramics: (a) x=0.05, (b) x=0.1, (c) x=0.15, (d) x=0.2

图9. NN-x(BNT-BF) (0.05≤x≤0.2)陶瓷: (a) 在最大外加电场作用下的P-E电路; (b) Pmax, Pr和ΔP随x的变化; (c) Wrec和η随x的变化

Figure 9. NN-x(BNT-BF) (0.05≤x≤0.2) ceramics: (a) P-E loops under maximum applied electric field; (b) variation of Pmax and Pr, ΔP with x; (c) variation of Wrec and η with x

图10. NN-0.2(BNT-BF)陶瓷: (a) 不同电场下的P-E电路; (b) Pmax, Pr和ΔP随电场的变化; (c) Wrec和η随电场的变化

Figure 10. NN-0.2(BNT-BF) ceramics: (a) P-E loops under different electric fields; (b) variation of Pmax, Pr and ΔP with electric fields; (c) variation of Wrec and η with electric fields

图11. NN-0.2(BNT-BF)陶瓷: (a) 在200 kV/cm下, 与温度相关的单极P-E回线; (b) Pmax和Pr随温度的变化; (c) Wrec和η随温度的变化

Figure 11. NN-0.2(BNT-BF) ceramics: (a) Temperature-dependent P-E loops at 200 kV/cm; (b) variation of Pmax and Pr values with temperature; (c) variation of Wrec and η values with temperature

图12. NN-0.2(BNT-BF)陶瓷: (a) 欠阻尼充放电电流曲线; (b) Imax, CD和PD随电场变化情况; (c) 过阻尼充放电电流曲线; (d) Imax, t0.9和Wd随电场的变化情况; (e) Wd随时间变化曲线

Figure 12. NN-0.2(BNT-BF) ceramics: (a) Underdamped charge-discharge current curves; (b) Imax, CD and PD variation with electric fields; (c) overdamped charge-discharge current curves; (d) variation of Imax, t0.9 and Wd with electric fields; (e) Wd with time curves

Composition	C_D/(A·cm⁻²)		P_D/(MW·cm⁻³)	W_d/(J·cm⁻³)	E/(kV·mm⁻¹)	t_0.9/ns	Ref.
0.78NaNbO₃-0.22Bi(Mg_2/3Ta_1/3)O₃	537.9		37.7	0.587	14	23	[40]
0.91NaNbO₃-0.09Bi(Zn_0.5Ti_0.5)O₃	356		20	0.48	11	250	[30]
0.85NaNbO₃-0.15Bi(Mg_2/3Nb_1/3)NbO₃	382		19	—	10	—	[41]
0.8(0.65Bi_0.5Na_0.5TiO₃-0.35Bi_0.2Sr_0.7TiO₃)-0.2BaSnO₃		600.13	38.73	0.8	12	186.4	[42]
0.5Na_0.5Bi_0.5TiO₃-0.5Sr_0.7Bi_0.2TiO₃	350		245	0.95	35	—	[43]
0.6(Bi_0.5K_0.5)TiO₃-0.3BaTiO₃-0.1NaNbO₃	103.2		2.4	2.07	22	130	[44]
0.94(Ba_0.3Sr_0.7)_0.35(Bi_0.5Na_0.5)_0.65TiO₃-0.06NaNbO₃	262		2.65	0.55	8	800	[45]
Pb_0.94La_0.04[(Zr_0.52Sn_0.48)_0.84Ti_0.16]O₃	143.8		2.4	0.38	4	—	[46]
0.8NaNbO₃-0.2(0.3Bi_0.5Na_0.5TiO₃-0.7BiFeO₃)	406		49	1.2	12	35	This work

表2. NN-0.2(BNT-BF)陶瓷与其他几种陶瓷的充放电性能比较

Table 2. Comparison of charge-discharge performance between NN-0.2(BNT-BF) ceramics and several other ceramics

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(1-x)NaNbO₃-x(0.3Bi_0.5Na_0.5TiO₃-0.7BiFeO₃)陶瓷的介电以及储能性能研究

Dielectric and Energy Storage Properties of (1-x)NaNbO₃-x(0.3Bi_0.5Na_0.5TiO₃-0.7BiFeO₃) Ceramics

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