Preparation of Zr-doped BaTiO3 dielectric ceramics by solution combustion synthesis and its energy storage performance
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摘要: 介电陶瓷电容器具有超高的功率密度和超快的充放电速度，在能量回收系统、脉冲大功率领域等具有重要的应用前景。以硝酸钡、钛酸丁酯、硝酸氧锆、甘氨酸以及硝酸为原料，柠檬酸为络合剂，硝酸锰为助烧剂，采用溶液燃烧法制备了Zr掺杂的 BaTi(1-x)ZrxO3(BTZx)介电陶瓷。分别采用 X 射线衍射仪和扫描电子显微镜对BTZx介电陶瓷样品进行了物相和微观形态分析。利用精密阻抗分析仪和铁电分析仪研究了BTZx 介电陶瓷样品的介电和储能性能。研究结果表明，Zr4+的引入细化了陶瓷晶粒，提高了击穿强度,增加了离子混乱度，有效减小了剩余极化。当x=0.20时，获得优异的储能性能： 在350 kV/cm下，可释放能量密度和储能效率分别达到 1.60 J/cm3 和 88.5%。Abstract: Dielectric ceramic capacitors have important application prospects in energy recovery systems and pulse power fields due to their ultrahigh power density and ultrafast charging- discharging speed. In this paper, Zr-doped BaTi(1-x)ZrxO3 (BTZx) dielectric ceramics were prepared by solution combustion synthesis with barium nitrate, butyl titanate, zirconium nitrate, glycine and nitric acid as raw materials, citric acid as complexing agent and manganese nitrate as sintering aid. The crystalline structure and microscopic morphologies of BTZx dielectric ceramic samples were analyzed by X-ray diffractometer and scanning electron microscope, respectively. The dielectric and energy storage properties of the BTZx dielectric ceramic samples were investigated using a precision impedance analyzer and a ferroelectric analyzer. The results show that the introduction of Zr4+ refines the ceramic grains, improves the breakdown strength, increases the ionic disorder, and effectively reduces the remanent polarization. When x=0.20, excellent energy storage performance is obtained: at 350 kV/cm, the recoverable energy density and energy storage efficiency reach 1.60 J/cm3 and 88.5%, respectively.
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图 1 (a) BTZx介电陶瓷样品的XRD衍射图谱；(b) BTZx介电陶瓷样品在衍射角(2θ)为 44°~46°的衍射图谱
Figure 1. (a) XRD patterns of the BTZx samples; (b) The diffraction patterns of BTZx samples at the diffraction angles (2θ) of 44°~46°
图 2 (a)～(d)分别为x=0.10, 0.14, 0.20, 0.24的陶瓷SEM形貌，（e）～(h)为相应的晶粒尺寸分布
Figure 2. (a)～(d) SEM images of ceramics with x=0.10, 0.14, 0.20, 0.24, respectively，（e）～(h) is the corresponding average grain size distribution
图 3 室温下BTZx介电陶瓷的介电常数和介电损耗随频率的变化
Figure 3. The spectrum of dielectric constant and dielectric loss of BTZx as a function of frequency at room temperature
图 4 (a) BTZx介电陶瓷在10 Hz、 150 kV/cm下的双极电滞回线; (b) 150 kV/cm电场下对应的 Pmax、Pr和 Pmax−Pr变化
Figure 4. (a) The bipolar P-E loops of BTZx at 10 Hz under 150 kV/cm; (b) Corresponding changes of Pmax, Pr and Pmax−Pr under 150 kV/cm
图 5 (a)BTZx介电陶瓷在10 Hz不同击穿电场下的单极电滞回线; (b)击穿电场下储能性能随x的演变
Figure 5. (a) The unipolar P-E loops of BTZx at different breakdown electric fields at 10 Hz; (b) The evolution of energy storage performance with x under breakdown electric fields
图 6 (a) BTZ0.20在不同电场条件下的单极电滞回线; (b)不同电场条件下的极化特性; (c) 不同电场下BTZ0.20的储能特性
Figure 6. (a) Variations of the unipolar P-E loops of BTZ0.20 with different electric fields; (b) The polarization characteristics of BTZ0.20 under different electric fields; (c) Energy storage properties of BTZ0.20 under different electric fields
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