Energy-storage Behavior Of Lead-based Antiferroelectric Ceramics Preparated By Tape-casting Method

PbZrO₃（PZ）is a lead-based antiferroelectric material that has received extensive attention and research due to its high dielectric constant,electric field induced phase transition,high polarization value after phase transition,and high Curie temperature.Coupled with the adjustable perovskite phase structure and dielectric tunability,PZ-based antiferroelectric materials have received extensive attention,and have been widely developed and used in energy storage capacitor devices due to their excellent energy storage properties.In this paper,the PZ and PZ-based antiferroelectric ceramics were prepared by the tape-casting method.The dielectric properties and energy-storage behaviors of PZ ceramics were investigated.The effects of different ions-doping and different doping contents on the energy-storage properties of PZ-based antiferroelectric ceramics were investigated.The purpose was to fabricate high quality dielectric ceramic materials with high energy-storage properties.At the same time,the effects of different ions-doping and different doping amount on the phase structure,microstructure,dielectric properties and breakdown strength of PZ-based antiferroelectric ceramics were also studied.First of all,the component PbZrO₃ was selected and a high quality ceramic was prepared by tape-casting method.It was found that the forward and backward phase transition fields E_AFE-FE and E_FE-AFE of PZ ceramic were 225 kV/cm and 165 kV/cm,respectively,and the breakdown field strength was 272 kV/cm.The dielectric constant was 210 and the dielectric loss was less than 0.1.As a result,through integrating the polarization-electric hysteresis loops,the highest energy-storage density obtained in the PZ ceramic was 6.7 J/cm³,and the corresponding energy-storage efficiency was 71.7%.Integrating the current curves tested by the pulse discharge,at 270 kV/cm,the maximum energy-storage density of the ceramic was 4.45 J/cm³ and 90%of the total energy-storage density can be released within 216 ns.Then,high quality ceramics with component of(Pb_1-x-x La_x)(Zr_0.98Ti_0.02)O₃（x=0.02,0.04,0.06）were prepared by tape-casting method.The stability of the orthorhombic antiferroelectric phase in ceramics was improved by adjusting the amount of La³⁺doping in the composition,thereby the forward and backward phase transition field strength of the ceramics were increased while the differences of them were reduced,under the premise that the saturation polarization value were slightly reduced.At the same time,an appropriate amount of La³⁺doping will increase the breakdown field strength of the ceramics.It was found that when the doping amount of La³⁺was 0.04 mol%,the forward and backward phase transition fields E_AFE-FE and E_FE-AFE of ceramics were 300 kV/cm and260 kV/cm,respectively,and the breakdown field strength was 345 kV/cm.The ceramic had a dielectric constant of 700 and a dielectric loss of less than 0.03.As a result,through integrating the polarization-electric hysteresis loops,the highest energy-storage density obtained in the ceramic was 9.84 J/cm³ and the corresponding energy-storage efficiency was as high as 82.2%.Through integrating the current curves tested by the pulse discharge,the maximum energy-storage density of the ceramic was 5.28 J/cm³ at 300 kV/cm,and90%of the total energy-storage density can be released within 125 ns.Finally,high quality ceramics with components of(Pb_0.96La_0.04)(Zr_1-yTi_y)O₃（y=0.01,0.02,0.03,0.04,0.05）were prepared by tape-casting method.The stability of the orthorhombic antiferroelectric phase in ceramics was improved by controlling the ion-doping amount of Ti⁴⁺in the composition,thereby enhancing the forward and backward phase transition field strength of the ceramics,under the premise that the saturation polarization value were not declined.At the same time,an appropriate amount of Ti⁴⁺doping will increase the breakdown field strength of the ceramics.It was found that when the doping amount of Ti⁴⁺was 0.01 mol%,the breakdown field strength of ceramic was413 kV/cm,whic was higher 19.7%than that of the ceramic with 0.02 mol%Ti⁴⁺.At 395kV/cm,the forward and backward phase transition fields E_AFE-FE and E_FE-AFE of ceramics were 300 kV/cm and 260 kV/cm,respectively.Calculated by polarization-electric hysteresis loops,the highest energy-storage density of the ceramic was 11.38 J/cm³ and the corresponding energy-storage efficiency was 79.2%at 395 kV/cm.Integrating the current curves tested by pulse discharge,at 350 kV/cm,the ceramic had a energy-storage density of 6.19 J/cm³ and 90%of the total energy-storage density can be released within70 ns.