In this work, we found that the defreezing coexistent glassy ferroelectric states hold significant potential for achieving superior energy storage performance, especially under low fields, by using phase field simulations and experimental approaches. A remarkable room-temperature energy recoverable storage density Wr exceeding 2.7 J/cm3 with a high efficiency η surpassing 80% under a low electric field of 170 kV/cm was obtained in the x = 6-12% compositions of x[Bi(Mg2/3Nb1/3)O3]-(1-x)[0.94(Bi0.5Na0.5)TiO3-0.06BaTiO3-1%MnO2] (BNBT-BMN) ceramics due to the combination of low Pr and high Pm of the coexistent ferroelectric glasses. Intriguingly, the superior Wr and η of the coexistent state of glasses can also be maintained in a wide temperature range of 293-430 K, indicating the excellent thermal stability of the energy storage behavior. Importantly, the Wr and η of this glass coexistent composition increase upon heating from room temperature to 360 K due to the defreezing process, leading to maximum Wr ∼ 2.9 J/cm3 with high efficiency η ∼ 90% of x = 10% at 360 K. When considering both energy storage behavior and thermal stability under low fields (<250 kV/cm), the BNBT-BMN ceramics outperform nearly all lead-free counterparts available today. Consequently, our work not only expands the research scope of ferroic glasses but also establishes a new paradigm for developing superior lead-free dielectrics suitable for high-temperature energy storage devices.
Keywords: energy storage effect; ferroelectric glasses; lead-free dielectrics; low driven fields; phase coexistence; thermal stability.