The quest for lead-free ferroelectric ceramics with superior pyroelectric properties and high energy storage efficiency under low electric fields, remains a crucial challenge. In this study, a detailed investigation was conducted on Ba0.95Ca0.05Ti0.908Zn0.002Sn0.08Zr0.01O3 (BCTSZZn) ceramic, synthesized via the conventional solid-state reaction method. X-ray diffraction (XRD) and Raman spectroscopy analyses confirmed the presence of a morphotropic phase boundary (MPB) at room temperature, characterized by the coexistence of orthorhombic and tetragonal phases. Dielectric characterization revealed a diffuse phase transition. The piezoelectric response, domain dynamics, and microstructural features were also examined. Based on Vopsaroiu’s model, the nucleation domain’s critical volume (V) and the activation energy per critical volume (WB = WBV) were determined. Notably, BCTSZZn exhibited a recoverable energy density (Wrec) of 97.85 kJ/m³ and an exceptional energy efficiency (η) of 81.89% under a modest electric field of 30 kV/cm. Various figures of merit were evaluated, yielding Fi = 514 pm/V, Fv = 0.00713 m2C− 1, Fe= 18.55 Jm−3K− 2 and Fe = 3.664 pm3J− 1. The thermal energy harvesting capability (ND) was further assessed using the Olsen cycle. Dynamic hysteresis scaling analysis revealed two distinct power-law dependencies for the hysteresis area (⟨A⟩) and Wrec with increasing electric field, highlighting changes in domain switching dynamics. Additionally, temperature-dependent scaling laws were established for key ferroelectric parameters, including ⟨A⟩, coercive field (Ec), and remnant polarization (Pr). The back-switching polarization (Pbc) was analyzed using the thermal activation model, offering a deeper understanding of thermal activation effects on polarization reversal. These findings position BCTSZZn ceramic as a highly promising candidate for advanced energy storage and thermal energy harvesting applications, particularly in next-generation pyroelectric devices and environmentally friendly energy conversion systems. Corresponding author: *E-mail: kacem.hend@gmail.com. Tel: +21,692,188,163. **E-mail: a.jbeli@mu.edu.sa.

Investigation of dynamic scaling behavior, pyroelectric energy storage and figures of merit of BCTSZZn lead-free ferroelectric ceramic

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发表日期：

2026年6月22日

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Hend Kacem,
Sonia Soltani,
Anouar Jbeli,
H. Marzougui,
Abdullah M. Aldukhayel,
Z. Sassi,
J. Dhahri

摘要

The quest for lead-free ferroelectric ceramics with superior pyroelectric properties and high energy storage efficiency under low electric fields, remains a crucial challenge. In this study, a detailed investigation was conducted on Ba_0.95Ca_0.05Ti_0.908Zn_0.002Sn_0.08Zr_0.01O₃ (BCTSZZn) ceramic, synthesized via the conventional solid-state reaction method. X-ray diffraction (XRD) and Raman spectroscopy analyses confirmed the presence of a morphotropic phase boundary (MPB) at room temperature, characterized by the coexistence of orthorhombic and tetragonal phases. Dielectric characterization revealed a diffuse phase transition. The piezoelectric response, domain dynamics, and microstructural features were also examined. Based on Vopsaroiu’s model, the nucleation domain’s critical volume (V*) and the activation energy per critical volume (W_B^* = W_BV^*) were determined. Notably, BCTSZZn exhibited a recoverable energy density (W_rec) of 97.85 kJ/m³ and an exceptional energy efficiency (η) of 81.89% under a modest electric field of 30 kV/cm. Various figures of merit were evaluated, yielding F_i = 514 pm/V, F_v = 0.00713 m²C^− 1, F_e= 18.55 Jm⁻³K^− 2 and F_e* = 3.664 pm³J^− 1. The thermal energy harvesting capability (N_D) was further assessed using the Olsen cycle. Dynamic hysteresis scaling analysis revealed two distinct power-law dependencies for the hysteresis area (⟨A⟩) and W_rec with increasing electric field, highlighting changes in domain switching dynamics. Additionally, temperature-dependent scaling laws were established for key ferroelectric parameters, including ⟨A⟩, coercive field (E_c), and remnant polarization (P_r). The back-switching polarization (P_bc) was analyzed using the thermal activation model, offering a deeper understanding of thermal activation effects on polarization reversal. These findings position BCTSZZn ceramic as a highly promising candidate for advanced energy storage and thermal energy harvesting applications, particularly in next-generation pyroelectric devices and environmentally friendly energy conversion systems. Corresponding author: *E-mail: kacem.hend@gmail.com. Tel: +21,692,188,163. **E-mail: a.jbeli@mu.edu.sa.