氧化镧掺杂铌酸钾钠陶瓷的电、光性能研究

doi:10.15541/jim20210297

无机材料学报 ›› 2022, Vol. 37 ›› Issue (5): 520-526.DOI: 10.15541/jim20210297

所属专题：【信息功能】电介质材料；【信息功能】透明陶瓷与光学晶体

氧化镧掺杂铌酸钾钠陶瓷的电、光性能研究

肖舒琳¹(), 戴中华¹(), 李定妍¹, 张凡博¹, 杨利红¹, 任晓兵²

1. 西安工业大学光电工程学院, 陕西省薄膜技术与光学检测重点实验室, 西安 710021
2. 西安交通大学前沿技术研究院, 西安 710049

收稿日期:2021-05-11 修回日期:2021-07-09 出版日期:2022-05-20 网络出版日期:2021-08-20
通讯作者: 戴中华, 教授. E-mail: zhdai@mail.xjtu.edu.cn
作者简介:肖舒琳(1998-), 女, 硕士研究生. E-mail: 1319643700@qq.com
基金资助:
国家自然科学基金(51831006);国家自然科学基金(51431007);陕西省科技计划(2020GY-311);西安市智能兵器重点实验室基金(2019220514SYS020CG042)

Electrical and Optical Property of Lanthanum Oxide Doped Potassium Sodium Niobate Ceramics

XIAO Shulin¹(), DAI Zhonghua¹(), LI Dingyan¹, ZHANG Fanbo¹, YANG Lihong¹, REN Xiaobing²

1. Shaanxi Province Key Laboratory of Thin Films Technology & Optical Test, School of Optoelectronic Engineering, Xi'an Technological University, Xi'an 710032, China;
2. Frontier Institute of Science and Technology, Xi'an Jiaotong University, X'ian 710049, China

Received:2021-05-11 Revised:2021-07-09 Published:2022-05-20 Online:2021-08-20
Contact: DAI Zhonghua, professor. E-mail: zhdai@mail.xjtu.edu.cn
About author:XIAO Shulin (1998-), female, Master candidate. E-mail: 1319643700@qq.com
Supported by:
National Natural Science Foundation of China(51831006);National Natural Science Foundation of China(51431007);Science and Technology Project of Shaanxi Province(2020GY-311);Xi’an Key Laboratory of Intelligence(2019220514SYS020CG042)

摘要/Abstract

摘要：

铌酸钾钠(K_0.5Na_0.5NbO₃, KNN)基陶瓷具有充放电速度快、透明度高、应用温度范围宽、使用寿命长等优点, 在脉冲功率器件等领域具有广阔的应用前景。通过改性技术提高铌酸钾钠基陶瓷的电、光性能是该方向的研究热点。本研究采用固相法制备0.825(K_0.5Na_0.5)NbO₃-0.175Sr_1-3_x_/2La_x(Sc_0.5Nb_0.5)O₃(x=0, 0.1, 0.2, 0.3)陶瓷(简称0.825KNN- 0.175SLSN), 研究La₂O₃掺杂对其相结构、微观形貌、光学、介电、铁电及储能性能的影响。研究结果表明: 0.825KNN- 0.175SLSN陶瓷具有高对称性的伪立方相结构; 随着La₂O₃掺杂量增大, 陶瓷的平均晶粒尺寸减小, 相变温度(T_m)及饱和极化强度(P_max)增大, 达到峰值后下降。在x=0.3时, 该体系陶瓷表现出优异的透明性, 在可见光波长(780 nm)及近红外波长(1200 nm)范围内透过率分别达65.2%及71.5%, 同时实现了310 kV/cm的击穿场强和1.85 J/cm ³的可释放能量密度。

关键词: 铌酸钾钠, 无铅透明陶瓷, 透过率, 储能性能

Abstract:

Potassium sodium niobate (K_0.5Na_0.5NbO₃, KNN) based ceramics can be widely used for pulsed power systems due to their fast charge-discharge rate, high transparency, wide range of working temperature, and long cycle life. Improving the electrical and optical property of KNN-based ceramics through modification is a research hotspot in this field. 0.825(K_0.5Na_0.5)NbO₃-0.175Sr_1-3_x_/2La_x(Sc_0.5Nb_0.5)O₃(x=0, 0.1, 0.2, 0.3) (0.825KNN- 0.175SLSN) ceramics were synthesized by solid state method. The effect of La₂O₃ doping on the phase structure, microstructure, optical property, dielectric property, ferroelectric property and energy storage property of the ceramic was studied. The results indicated that the structure of 0.825KNN-0.175SLSN ceramics is pseudo-cubic phase with high symmetry. With increment of La₂O₃content, the average grain size of 0.825KNN-0.175SLSN ceramics decreased, and the phase transition temperature (T_m) and saturation polarization intensity (P_max) increased and then decreased. 0.825KNN-0.175SLSN ceramics exhibit excellent transparency at x=0.3, the transmittance in the visible wavelength (780 nm) and near-infrared wavelength (1200 nm) ranges reaches 65.2% and 71.5%, respectively. The dielectric breakdown strength of 310 kV/cm and a recoverable energy density of 1.85 J/cm ³ are achieved at x=0.3.

Key words: potassium sodium niobate, lead-free transparent ceramics, transmittance, energy storage property

中图分类号:

TQ174

肖舒琳, 戴中华, 李定妍, 张凡博, 杨利红, 任晓兵. 氧化镧掺杂铌酸钾钠陶瓷的电、光性能研究[J]. 无机材料学报, 2022, 37(5): 520-526.

XIAO Shulin, DAI Zhonghua, LI Dingyan, ZHANG Fanbo, YANG Lihong, REN Xiaobing. Electrical and Optical Property of Lanthanum Oxide Doped Potassium Sodium Niobate Ceramics[J]. Journal of Inorganic Materials, 2022, 37(5): 520-526.

图/表 8

图1 0.825KNN-0.175SLSN陶瓷密度与La含量的关系图

Fig. 1 Variation of density for the 0.825KNN-0.175SLSN ceramics with different content of La

图2 0.825KNN-0.175SLSN陶瓷在室温下2θ的XRD谱图

Fig. 2 XRD patterns of the 0.825KNN-0.175SLSN ceramics at room temperature

图3 0.825KNN-0.175SLSN陶瓷室温下自然表面的扫描电镜照片

Fig. 3 SEM micrographs of the original surfaces of 0.825KNN-0.175SLSN (a) x=0; (b) x=0.1; (c) x=0.2; (d) x=0.3

图4 0.825KNN-0.175SLSN陶瓷的透过率图 (a)和0.825KNN-0.175SLSN陶瓷的(αhν)2随hν的变化关系图(b)

Fig. 4 Transmission spectra (a) of 0.825KNN-0.175SLSN ceramic, with inset showing photographs of the 0.3 mm specimens, and plots (b) of (αhν)2 and hν of the 0.825KNN-0.175SLSN ceramic with x=0.3

图5 0.825KNN-0.175SLSN陶瓷样品的介电性能-温度关系图 (a~d)和0.825KNN-0.175SLSN陶瓷的Tm, εm与La掺杂含量关系图(e)

Fig. 5 Temperature dependence of the dielectric properties (a-d), Tm and εm (e) of 0.825KNN-0.175SLSN ceramics

图6 0.825KNN-0.175SLSN陶瓷在150 kV/cm电场下的单极P-E曲线

Fig. 6 P-E loops of 0.825KNN-0.175SLSN ceramics at selected applied electric fields Colorful figures are available on website

图7 不同La掺杂含量陶瓷的Pmax和Pr

Fig. 7 Pmax and Pr of 0.825KNN-0.175SLSN ceramics as a function of x

图8 0.825KNN-0.175SLSN陶瓷在击穿场强下的单极P-E曲线 (a~d), 0.825KNN-0.175SLSN陶瓷的W、Wrec 与x的关系曲线(e), 0.825KNN-0.175SLSN陶瓷的η和Eb与x的关系曲线(f)

Fig. 8 Unipolar P-E hysteresis loops (a-d) of 0.825KNN-0.175SLSN ceramics under different electric fields, variation (e) of W and Wrec, for the 0.825KNN-0.175SLSN ceramics with different x, and variation (f) of η and Eb for the 0.825KNN-0.175SLSN ceramics with different x

参考文献 31

[1]	YAO Z H, SONG Z, HAO H, et al.. Homogeneous/inhomogeneous- structured dielectrics and their energy-storage performances. Advanced Materials, 2017,29(20):1601727.
[2]	YANG L, KONG X, LI F, et al.. Perovskite lead-free dielectrics for energy storage applications. Progress in Materials Science, 2019,102:72-108.
[3]	WANG H, LIU Y, YANG T, et al.. Ultrahigh energy-storage density in antiferroelectric ceramics with field-induced multiphase transitions. Advanced Functional Materials, 2019,29(7):1807321.
[4]	ZHAO P, WANG H, WU L, et al.. High-performance relaxor ferroelectric materials for energy storage applications. Advanced Energy Materials, 2019,9(17):1803048.
[5]	LI J T, BAI Y, QIN S Q. Direct and indirect characterization of electrocaloric effect in (Na, K)NbO₃ based lead-free ceramics. Applied Physics Letters, 2016,109(16):162902-162904.
[6]	WANG X J, WU J G, BRAHIM D. Enhanced electrocaloric effect near polymorphic phase boundary in lead-free potassium sodium niobate ceramics. Applied Physics Letters, 2017,110(6):063904.
[7]	YANG Z T, GAO F, DU H L, et al.. Grain size engineered lead-free ceramics with both large energy storage density and ultrahigh mechanical properties. Nano Energy, 2019,58:768-777.
[8]	DU H L, YANG Z T, GAO F, et al.. Lead-free nonlinear dielectric ceramics for energy storage applications: current status and challenges. Journal of Inorganic Materials, 2018,33(10):14-26.
[9]	YANG Z T, DU H L, QU S B, et al.. Significantly enhanced recoverable energy storage density in potassium-sodium niobatebased lead free ceramics. Journal of Materials Chemistry A, 2016,4(36):13778-13785.
[10]	SNOW C S. Fabrication of transparent electrooptic PLZT ceramics by atomosphere sintering. Journal of the American Ceramic Society, 1973,56(2):91-96.
[11]	LI G R, RUAN W, ZENG J T, et al.. The effect of domain structures on the transparency of PMN-PT transparent ceramics. Optical Materials, 2013,35(4):722-726.
[12]	LU X P, XU J W, LING Y, et al.. Energy storage properties of (Bi_0.5Na_0.5)_0.93Ba_0.07TiO₃ lead-free ceramics modified by La and Zr co-doping. Journal of Materiomics, 2016,2(1):87-93.
[13]	WANG Y F, LV Z L, HUI X, et al. High energy-storage properties of [(Bi_1/2Na_1/2)_0.94Ba_0.06]La _(1-_x₎Zr_xTiO₃ lead-free anti-ferroelectric ceramics. Ceramics International, 2014,40(3):4323-4326.
[14]	REN X, JIN L, PENG Z, et al.. Regulation of energy density and efficiency in transparent ceramics by grain refinement. Chemical Engineering Journal, 2020,390:124566.
[15]	ZHANG M, YANG H, LI D, et al.. Excellent energy density and power density achieved in K_0.5Na_0.5NbO₃-based ceramics with high optical transparency. Journal of Alloys and Compounds, 2020,829:154565.
[16]	HEARTLING G S. Improved hot-pressed electrooptic ceramics in the (Pb,La)(Zr,Ti)O₃ system. Journal of the American Ceramic Society, 1973,56(2):91-96.
[17]	SONG Z Z, ZHANG Y C, LU C J, et al.. Fabrication and ferroelectric/ dielectric properties of La-doped PMN-PT ceramics with high optical transmittance. Ceramics International, 2017,43(4):3720-3725.
[18]	ANDREAS K, THOMAS H, JEN K. Transmission physics and consequenees for materials seleetion, manufacturing, and applications. Journal of the European Ceramic Soeiety, 2009,29(2):207-221.
[19]	PEELEN J, METSELAAR R. Light scattering by pores in poly- crystalline materials. Journal of Applied Physics, 1974,45(1):216-220.
[20]	KRELL A, BLANK P, MA H, et al.. Transparent sintered corundum with high hardness and strength. Journal of the American Ceramic Society, 2010,86(1):12-18.
[21]	FU J, ZUO R Z, XU Y D, et al.. Investigations of domain switching and lattice strains in (Na,K)NbO₃-based lead-free ceramics across orthorhombic-tetragonal phase boundary. Journal of the European Ceramic Society, 2017,37(3):975-983.
[22]	CHENG X J, GOU Q, WU J G, et al.. Dielectric, ferroelectric, and piezoelectric properties in potassium sodium niobate ceramics with rhombohedral-orthorhombic and orthorhombic-tetragonal phase boundaries. Ceramics International, 2014,40(4):5771-5779.
[23]	LIN C, WU X, LIN M, et al.. Optical, luminescent and optical temperature sensing properties of (K_0.5Na_0.5)NbO₃-ErBiO₃ transparent ceramics. Journal of Alloys & Compounds, 2017,706:156-163.
[24]	GENG Z M, LI K, SHI D L, et al.. Effect of Sr and Ba-doping in optical and electrical properties of KNN based transparent ceramics. Journal of Materials Science: Materials in Electronics, 2015,26(9):6769-6775.
[25]	LIU Z Y, FAN H Q, PENG B L. Enhancement of optical transparency in Bi₂O₃-modified (K_0.5Na_0.5)_0.9Sr_0.1Nb_0.9Ti_0.1O₃ ceramics for electro-optic applications. Journal of Materials Science, 2015,50(24):7958-7966.
[26]	WOOTEN F. Optical properties of solids. American Journal of Physics, 1973,41(7):939-940.
[27]	CHAI Q Z, YANG D, ZHAO X M, et al.. Lead-free (K,Na)NbO₃- based ceramics with high optical transparency and large energy storage ability. Journal of the American Ceramic Society, 2018,101(6):2321-2329.
[28]	QU B Y, DU H L, YANG Z T. Lead-free relaxor ferroelectric ceramics with high optical transparency and energy storage ability. Journal of Materials Chemistry C, 2016,4(9):1795-1803.
[29]	DAI Z H, XIE J L, CHEN Z B, et al.. Improved energy storage density and efficiency of (1-x)Ba_0.85Ca_0.15Zr_0.1Ti_0.9O₃-xBiMg_2/3Nb_1/3O₃ lead-free ceramics. Chemical Engineering Journal, 2021,410:128341.
[30]	DAI Z H, XIE J L, LIU W G, et al. An effective strategy to achieve excellent energy storage properties in lead-free BaTiO₃ based bulk ceramics. ACS Applied Materials & Interfaces, 2020,12(27):30289-30296.
[31]	DAI Z H, XIE J L, FAN X, et al. Enhanced energy storage properties and stability in Sr(Sc_0.5Nb_0.5)O₃ modified 0.65BaTiO₃- 0.35Bi_0.5Na_0.5TiO₃ ceramics. Chemical Engineering Journal, 2020,397:125520.

氧化镧掺杂铌酸钾钠陶瓷的电、光性能研究

Electrical and Optical Property of Lanthanum Oxide Doped Potassium Sodium Niobate Ceramics

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 8

参考文献 31

相关文章 15

编辑推荐

Metrics

本文评价

[1]	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.
[2]	王通,王渊浩,杨海波,高淑雅,王芬,鲁雅文. BaTiO₃-ZnNb₂O₆陶瓷介电及储能性能研究[J]. 无机材料学报, 2020, 35(4): 431-438.
[3]	林德宝, 范灵聪, 丁毛毛, 谢建军, 雷芳, 施鹰. 氧化锌透明陶瓷光学透过模型构建与实验验证[J]. 无机材料学报, 2019, 34(8): 851-856.
[4]	徐家跃, 梁肖肖, 金敏, 曾海波, KIMURAHideo, 胡皓阳, 邵和助, 申慧, 田甜, 李海霞. 移动区熔法生长全无机钙钛矿型CsPbBr₃晶体及其性能研究[J]. 无机材料学报, 2018, 33(11): 1253-1258.
[5]	凌云鹏, 闵嘉华, 梁小燕, 张继军, 杨柳青, 温旭亮, 张滢, 李明, 刘兆鑫, 王林军, 沈悦. 溶剂熔区移动法生长Cd_0.9Zn_0.1Te晶体的工艺优化研[J]. 无机材料学报, 2017, 32(9): 980-984.
[6]	王红燕, 张浩, 姜宏, 汪国庆, 熊春荣. 高可见光透过、高紫外截止镀膜玻璃的制备[J]. 无机材料学报, 2017, 32(7): 758-764.
[7]	王超, 陈静, 陈红丽, 侯育冬, 朱满康. 纳米铌酸钾钠陶瓷的制备及性能[J]. 无机材料学报, 2015, 30(1): 59-64.
[8]	耿志明, 李坤, 施东良, 施瑕玉, 黄海涛, 陈王丽华. 铌酸钾钠基透明上转换陶瓷材料制备及性能[J]. 无机材料学报, 2014, 29(12): 1265-1269.
[9]	王轲, 沈宗洋, 张波萍, 李敬锋. 铌酸钾钠基无铅压电陶瓷的现状、机遇与挑战[J]. 无机材料学报, 2014, 29(1): 13-22.
[10]	张志强, 刘志甫, 李永祥. 0.84(K_0.48Na_0.52)NbO₃-0.16K_0.56Li_0.38NbO_2.97无铅压电陶瓷的多层膜工艺研究[J]. 无机材料学报, 2014, 29(1): 23-27.
[11]	张东升, 田爱芬. 无铅压电陶瓷KNN常压烧结及其电学性能[J]. 无机材料学报, 2013, 28(9): 967-970.
[12]	江向平, 易文斌, 陈超, 涂娜, 李小红, 展红全. [(Na_xK(1–x))_0.985Bi_0.015](Nb_0.97Ti_0.03)O₃陶瓷的压电与介电性能研究[J]. 无机材料学报, 2013, 28(3): 326-330.
[13]	李月明, 肖祖贵, 沈宗洋, 王竹梅, 洪燕, 潘铁政, 吴芬. BaZrO₃掺杂对(K_0.49Na_0.51)_0.98Li_0.02(Nb_0.77Ta_0.18Sb_0.05)O₃无铅压电陶瓷的结构与电性能的影响[J]. 无机材料学报, 2013, 28(06): 629-634.
[14]	叶龙强, 张清华, 张雨露, 张欣向, 江波. 耐摩擦和高透过SiO₂/TiO₂/SiO₂-TiO₂增透膜的设计和制备[J]. 无机材料学报, 2012, 27(8): 871-875.
[15]	毛茂, 黄婉霞, 张雅鑫, 颜家振, 罗轶, 施奇武, 蔡靖涵. 钨掺杂二氧化钒薄膜的THz波段相变性能的研究[J]. 无机材料学报, 2012, 27(8): 891-896.