Superior energy storage efficiency through tailoring relaxor behavior and band energy gap in KNN-based ferroelectric ceramic capacitors

With the increasing demand of high-power and pulsed power electronic devices,environmental-friendly potassium sodium niobate((Na_(0.5)K_(0.5))NbO_(3),KNN)ceramic-based capacitors have attracted much attention in recent years owning to the boosted energy storage density(W_(rec)).Nevertheless,the dielectric loss also increases as the external electric field increases,which will generate much dissipated energy and raise the temperature of ceramic capacitors.Thus,an effective strategy is proposed to enhance the energy storage efficiency(η)via tailoring relaxor behavior and bad gap energy in the ferroelectric 0.9(Na_(0.5)K_(0.5))-NbO_(3)-0.1Bi(Zn_(2/3)(Nb_(x)Ta_(1−x))1/3)O_(3) ceramics.On the one hand,the more diverse ions in the B-sites owing to introducing the Ta could further disturb the long-range ferroelectric polar order to form the short−range polar nanoregions(PNRs),resulting in the highη.On the other hand,the introduction of Ta ions could boost the intrinsic band energy gap and thus improve the Eb.As a result,high Wrec of 3.29 J/cm^(3) and ultrahighηof 90.1%at the high external electric field of 310 kV/cm are achieved in x=0.5 sample.These results reveal that the KNN-based ceramics are promising lead-free candidate for high-power electronic devices.

[001]-texturing of(K,Na)NbO_(3)-based piezoceramics with a pseudocubic structure and their application to piezoelectric devices

0.96(K_(0.5)Na_(0.5-z)Li_(z))(Nb_(0.92)Sb_(0.08))O_(3)-0.04(Ca_(0.5)Sr_(0.5))ZrO_(3)[(KN_(0.5-z)L_(z))NS-CSZ]piezoceramics(0≤z≤0.04)were aligned in the[001]orientation using 3%(in mole)NaNbO_(3)templates with a large Lotgering factor(>97%).Their crystal structures transformed from the orthorhombic-pseudocubic(O-P)structure to the orthorhombic-tetragonal-pseudocubic(O-T-P)structure with an increasing z.The P structure was interpreted as a rhombohedral R3m structure.The piezoelectricity of the compositions increased after[001]-texturing,and the enhancement was proportional to the O phase quantity.The composition(z=0.03)exhibited the highest piezoelectric constant(d_(33);670 pC/N)and electromechanical coupling factor(k_(p);0.56).Piezoelectric energy harvesters were produced using the untextured and textured samples(z=0.03).The textured harvester delivered a large power density of 26.6 mW/mm^(3),which was larger than that of the untextured harvester owing to the enhanced kp and d_(33)×g_(33) of the textured piezoceramic.A multilayer actuator was produced using the textured sample(z=0.03),and it exhibited a large acceleration(44.2 G)and displacement(±3,730 mm)at±25 V.Therefore,the[001]-textured(KN_(0.47)L_(0.03))NS-CSZ piezoceramic is suitable for piezoelectric energy harvesters and actuators.

Optimizing the grain size and grain boundary morphology of (K,Na) NbO_(3)-based ceramics: Paving the way for ultrahigh energy storage capacitors

Relaxor dielectric ceramic capacitors are very attractive for high-power energy storage.However,the low breakdown strength severely restricts improvements to the energy storage density and practical application.Here,a strategy of designing small grain sizes and abundant amorphous grain boundaries is proposed to improve the energy storage properties under the guidance of phase field theory.0.925(K_(0.5)Na_(0.5))NbO_(3)-e0.075Bi(Zn_(2/3)(Ta_(0.5)Nb_(0.5))1/3)O_(3)(KNNe-BZTN)relaxor ferroelectric ceramic is taken as an example to verify our strategy.The grain sizes and grain boundaries of the KNNeBZTN ceramics are carefully controlled by the high-energy ball milling method and twoestep sintering strategy.Impedance analysis and diffusion reflectance spectra demonstrate that KNNeBZTN ceramics with a small grain size and abundant amorphous grain boundary exhibit a lower charge carrier concentration and higher band gap.As a consequence,the breakdown electric field of KNNeBZTN ceramics increases from 222 kV/cm to 317 kV/cm when the grain size is decreased from 410 nm to 200 nm,accompanied by a slightly degraded maximum polarization.KNNeBZTN ceramics with an average grain size of~250 nm and abundant amorphous grain boundaries exhibit optimum energy storage properties with a high recoverable energy density of 4.02 J/cm^(3) and a high energy efficiency of 87.4%.This successful local structural design opens up a new paradigm to improve the energy storage performance of other dielectric ceramic capacitors for electrical energy storage.

Low-temperature dielectric relaxation associated with NbO_6 octahedron distortion in antimony modified potassium sodium niobate ceramics

Although the antimony(Sb) has been widely used to modify potassium sodium niobate(KNN) ceramics for tailoring the phase structure and performance, the role of Sb still remains insufficiently understood,consequently hindering the understanding of the physical origin of high-performance KNN-based ceramics. Here, we combine the experiments and first-principles calculations to deeply reveal the effects of Sb on KNN ceramics. Our results reveal a re-entrant-like relaxation behavior near the rhombohedralorthorhombic(R-O) phase transition at the low content of Sb, which transforms into a canonical one at higher content of Sb. First-principles calculations show a significantly decreased difference in the bond length of six B-O bonds of Nb O6 octahedral in Sb-modified KNN ceramics compared to pristine KNN ceramics, responsible for the low-temperature re-entrant-like dielectric relaxation. Furthermore, the addition of Sb would soften the B-O repulsion and gradually break the long-range ferroelectric ordering,resulting in the occurrence of nanoscale domains and enhanced local heterogeneity. Finally, we find that the optimized piezoelectric properties are the trade-off between the long-range ferroelectric ordering and the local heterogeneity. Therefore, this work not only deeply reveals the effects of Sb on KNN ceramics from multi-scale perspectives but also helps the future composition design for achieving high piezoelectricity.