Large Electrocaloric Responsivity and Energy Storage Response in the Lead-Free Ba(Ge(x)Ti(1-x))O(3) Ceramics

Ferroelectric property that induces electrocaloric effect was investigated in Ba(Ge(x)Ti(1-x))O(3) ceramics, known as BTGx. X-ray diffraction analysis shows pure perovskite phases in tetragonal symmetry compatible with the P4mm (No. 99) space group. Dielectric permittivity exhibits first-order ferroelectric-paraelectric phase transition, confirmed by specific heat measurements, similar to that observed in BaTiO(3) (BTO) crystal. Curie temperature varies weakly as a function of Ge-content. Using the direct and indirect method, we confirmed that the adiabatic temperature change ΔT reached its higher value of 0.9 K under 8 kV/cm for the composition BTG6, corresponding to an electrocaloric responsivity ΔT/ΔE of 1.13 \texttimes 10(-6) K.m/V. Such electrocaloric responsivity significantly exceeds those obtained so far in other barium titanate-based lead-free electrocaloric ceramic materials. Energy storage investigations show promising results: stored energy density of ~ 17 mJ/cm(3) and an energy efficiency of ~ 88% in the composition BTG5. These results classify the studied materials as candidates for cooling devices and energy storage applications.