通过晶界工程提升Tm掺杂反铁电陶瓷储能性质  

Enhanced Energy Storage Properties in Tm-Doped Antiferroelectric Ceramics by Engineering Grain Boundaries

作　　者：徐立智 陈立明 赵启然 杨慧琳 丁健翔 XU Lizhi;CHEN Liming;ZHAO Qiran;YANG Huilin;DING Jianxiang(Research Center of Advanced Ceramic,School of Materials Science And Engineering,Anhui University of Technology,Maanshan 243002,Anhui,China)

机构地区：[1]安徽工业大学材料科学与工程学院先进陶瓷研究中心,安徽马鞍山243002

出　　处：《硅酸盐学报》2024年第4期1267-1276,共10页Journal of The Chinese Ceramic Society

基　　金：安徽省高等学校科学研究重点项目(2023AH051103);安徽省自然科学基金青年项目(2108085QE193);国家级大学生创新训练项目(202310360023)。

摘　　要：反铁电陶瓷材料由于其相变储能特性,在脉冲电容器领域引起广泛关注。然而,低的储能密度和储能效率难以实现器件的小型化,高功率化,阻碍了基于反铁电陶瓷脉冲电容器的实际应用。本工作采用流延法制备(Pb_((1–1.5x))Tm_(x))(Zr_(0.55)Sn_(0.44)Ti_(0.01))O_(3)(x=0.00、0.02、0.04、0.06)反铁电陶瓷,通过构建晶界阻抗策略,改善电学性能,提高击穿强度,进而达到提高其储能密度的目的。系统地研究了掺杂不同含量的Tm^(3+),对(Pb_((1–1.5x))Tm_(x))(Zr_(0.55)Sn0.44Ti_(0.01))O_(3)陶瓷的相结构,微观形貌,介电性能,储能特性,电学性能以及放电行为的影响。结果表明,随着Tm^(3+)含量的增加,晶粒逐步细化,界面数量增加,致使反铁电陶瓷由晶界–晶粒阻抗作用转变为晶界阻抗占主导作用。因此,陶瓷系统电阻提高,绝缘性增强,最终导致介电击穿(Eb=490 kV/cm)上升,获得了高的储能密度(W_(rec)=9.37 J/cm^(3)),高的储能效率(η=77%)以及较好的放电能量密度(W_(dis)=5.5 J/cm^(3))。此外,(Pb_((1–1.5x))Tm_(x))(Zr_(0.55)Sn_(0.44)Ti_(0.01))O_(3)陶瓷在30~120℃温度范围内,储能密度变化小于8%,具有良好的温度稳定性,是一种优异的高温脉冲功率电容器材料,为脉冲功率电容器的设计提供一种新的思路。Introduction The pulse power capacitors can be used in military,medical,and aerospace fields due to their high power density and rapid charge-discharge capabilities.Despite these advantages,limited energy storage capacity and efficiency become challenges in achieving miniaturization and high-power performance.Among dielectric energy storage materials,antiferroelectric materials are regarded as promising for high-performance pulse power capacitors due to their distinctive double hysteresis loops,lower residual polarization,and higher energy storage efficiency.However,the breakdown strength decreases due to non-uniform electric field when the resistance of ceramic grain is equal to that of grain boundary,resulting in a decrease of energy storage density.Therefore,the enhancement of grain boundary impedance plays a key role in improving the dielectric breakdown strength of the system.In this paper,(Pb_((1–1.5x))Tm_(x))(Zr_(0.55)Sn_(0.44)Ti_(0.01))O_(3)(x=0.00,0.02,0.04,0.06)antiferroelectric ceramics were prepared via tape casting.The strategy of grain boundary impedance was constructed via enhancing the grain boundary quantity.Methods Powders of Pb_(3)O_(4),Tm^(3)O_(2),ZrO_(2),SnO_(2),and TiO_(2) as raw materials were precisely weighed according to their chemical formulae after drying.The powders were mixed with alcohol and then ground in a ball mill for 24 h.Afterwards,the mixture was dried and pre-sintered at 850℃,and further ground in a ball mill for 24 h.The ground powders were mixed with toluene ethanol as a solvent,polyvinyl alcohol as an adhesive and butyl phthalate as a plasticizer.After 24 h milling,the mixture underwent degassing for 40 min,resulting in a slurry with an optimal fluidity.A flexible film with a thickness of 0.02 mm was produced via casting at a linear speed of 40 cm/min,and dried for 6 h.This film was then compressed into a block with the sizes of 10.0 mm×10.0 mm×0.5 mm.The samples were sintered in a muffle furnace via increasing the temperature from room temperature to 600℃for 12 h

关 键 词：反铁电陶瓷 储能特性 晶粒细化 晶界阻抗 

分 类 号：TQ174.75[化学工程—陶瓷工业]