Defect structure‐electrical property relationship in Mn‐doped calcium strontium titanate dielectric ceramics

Ca0.6Sr0.4TiO3 (CST) ceramics with different amounts of Mn dopant (0~2.0 mol%) were prepared by solid state reaction method. The electric field and temperature stability of energy storage performance was found to be greatly enhanced with moderate doped level of 0.5 mol%. The dielectric loss-frequency spectra revealed the existence and evolution of defect dipoles at elevated temperature, which was confirmed directly by electron paramagnetic resonance (EPR) spectra. The response of defect dipoles was characterized by thermally stimulated depolarization current (TSDC), where the activation energy and the concentration evolution of defect dipoles were calculated, with the highest values observed for 0.5% doped samples. The dissociation of defect dipoles and the movement of free Vo.. were analyzed by high temperature impedance spectra analysis, with the activation energy of 1.04~1.60 eV, and 0.5% doped samples also demonstrated the highest Ea. The relationship between microscopic defect structure and macroscopic electrical behavior was established in this work. This article is protected by copyright. All rights reserved.

[1]  Hanxing Liu,et al.  Effect of HfO2 addition as intergranular grains on the energy storage behavior of Ca0.6Sr0.4TiO3 ceramics , 2016 .

[2]  Tiandong Zhang,et al.  Defect dipole induced large recoverable strain and high energy-storage density in lead-free Na0.5Bi0.5TiO3-based systems , 2016 .

[3]  W. Fei,et al.  Large electrocaloric response and high energy-storage properties over a broad temperature range in lead-free NBT-ST ceramics , 2016 .

[4]  M. Lanagan,et al.  Improved Energy Storage Properties Accompanied by Enhanced Interface Polarization in Annealed Microwave‐Sintered BST , 2015 .

[5]  R. Zuo,et al.  Novel BiFeO3–BaTiO3–Ba(Mg1/3Nb2/3)O3 Lead-Free Relaxor Ferroelectric Ceramics for Energy-Storage Capacitors , 2015 .

[6]  Xiaoyong Wei,et al.  Dielectric and temperature stable energy storage properties of 0.88BaTiO3–0.12Bi(Mg1/2Ti1/2)O3 bulk ceramics , 2015 .

[7]  Li Tianming,et al.  Enhanced energy storage properties of NaNbO3 modified Bi0.5Na0.5TiO3 based ceramics , 2015 .

[8]  Wei Li,et al.  Enhanced energy-storage properties of (1-x)[(1-y)(Bi0.5Na0.5)TiO3-y(Bi0.5K0.5)TiO3]-x(K0.5Na0.5)NbO3 lead-free ceramics , 2015 .

[9]  Jun Yan,et al.  Chemical nature of giant strain in Mn-doped 0.94(Na0.5Bi0.5)TiO3–0.06BaTiO3 lead-free ferroelectric single crystals , 2014 .

[10]  D. P. Shay,et al.  Development and Characterization of High Temperature, High Energy Density Dielectric Materials to Establish Routes towards Power Electronics Capacitive Devices , 2014 .

[11]  D. Kim,et al.  Correlation between I (current)-V (voltage) characteristics and thermally stimulated depolarization current of Mn-doped BaTiO3 multilayer ceramic capacitor , 2013 .

[12]  S. Trolier-McKinstry,et al.  High‐Energy Density Dielectrics and Capacitors for Elevated Temperatures: Ca(Zr,Ti)O3 , 2013 .

[13]  Y. Han,et al.  Dielectric properties of Mg- and Mn-doped (Ba1−xSrx)(Ti1−yZry)O3 , 2013, Metals and Materials International.

[14]  C. Randall,et al.  High Temperature, High Energy Density Dielectrics for Power Electronics Applications , 2012 .

[15]  C. Randall,et al.  High Energy Density, High Temperature Capacitors Utilizing Mn-Doped 0.8CaTiO3–0.2CaHfO3 Ceramics , 2012 .

[16]  Hanxing Liu,et al.  Structure, Dielectric Properties and Temperature Stability of BaTiO3–Bi(Mg1/2Ti1/2)O3 Perovskite Solid Solutions , 2011 .

[17]  Xilin Xu,et al.  Robust BME Class-I MLCCs for Harsh-Environment Applications , 2011, IEEE Transactions on Industrial Electronics.

[18]  Jacob L. Jones,et al.  Processing of Manganese‐Doped [Bi0.5Na0.5]TiO3 Ferroelectrics: Reduction and Oxidation Reactions During Calcination and Sintering , 2011 .

[19]  R. Eichel.  Structural and dynamic properties of oxygen vacancies in perovskite oxides--analysis of defect chemistry by modern multi-frequency and pulsed EPR techniques. , 2011, Physical chemistry chemical physics : PCCP.

[20]  C. Randall,et al.  Difference between resistance degradation of fixed valence acceptor (Mg) and variable valence acceptor (Mn)-doped BaTiO3 ceramics , 2010 .

[21]  Qing Wang,et al.  High-temperature poly(phthalazinone ether ketone) thin films for dielectric energy storage. , 2010, ACS applied materials & interfaces.

[22]  Junjun Li,et al.  Dielectric characteristics of poly(ether ketone ketone) for high temperature capacitive energy storage , 2009 .

[23]  Bruno Allard,et al.  State of the art of high temperature power electronics , 2009 .

[24]  C. Randall,et al.  Thermally Stimulated Relaxation in Fe-Doped SrTiO3 Systems:I. Single Crystals , 2008 .

[25]  C. Randall,et al.  Thermally Stimulated Relaxation in Fe‐Doped SrTiO3 Systems: II. Degradation of SrTiO3 Dielectrics , 2008 .

[26]  R. Eichel.  Characterization of Defect Structure in Acceptor-Modified Piezoelectric Ceramics by Multifrequency and Multipulse Electron Paramagnetic Resonance Spectroscopy , 2008 .

[27]  A. Bos.  Theory of thermoluminescence , 2006 .

[28]  Seoncheol Cha,et al.  Effects of Mn doping on dielectric properties of Mg-doped BaTiO3 , 2006 .

[29]  Y. Han,et al.  Electrical Properties of Acceptor Doped BaTiO3 , 2004 .

[30]  J. Maier,et al.  Defect association in acceptor-doped SrTiO3: case study for Fe′TiV˙˙O and Mn″TiV˙˙O , 2003 .

[31]  R. Waser,et al.  dc Electrical Degradation of Perovskite‐Type Titanates: II, Single Crystals , 1990 .

[32]  J. Rödel,et al.  Degradation of Mn-doped BaTiO3 ceramic under a high d.c. electric field , 1984 .

[33]  R. A. Serway,et al.  Electron paramagnetic resonance of three manganese centers in reduced SrTiO 3 , 1977 .

[34]  A. Gibson,et al.  The Electron Trap Mechanism of Luminescence in Sulphide and Silicate Phosphors , 1948 .

[35]  Sheng Chao,et al.  Effects of Manganese Doping on the Dielectric Properties of Titanium Dioxide Ceramics , 2011 .

[36]  Wei-En Liu.  Impedance/thermally stimulated depolarization current and microstructural relations at interfaces in degraded perovskite dielectrics , 2009 .