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As an alternative to conventional vapor-compression refrigeration, cooling devices based on electrocaloric (EC) materials are environmentally friendly and highly efficient, which are promising in realizing solid-state cooling. Lead-free ferroelectric ceramics with competitive EC performance are urgently desirable for EC cooling devices. In the past few decades, constructing phase coexistence and high polarizability have been two crucial factors in optimizing the EC performance. Different from the external stress generated through heavy equipment and inner interface stress caused by complex interface structures, the internal lattice stress induced by ion substitution engineering is a relatively simple and efficient means to tune the phase structure and polarizability. In this work, we introduce low-radius Li + into BaZr 0.2 Ti 0.8 O 3 (BZT) to form a particular A-site substituted cell structure, leading to a change of the internal lattice stress. With the increase of lattice stress, the fraction of the rhombohedral phase in the rhombohedral-cubic (R-C) coexisting system and ferroelectricity are all pronouncedly enhanced for the Li 2 CO 3 -doped sample, resulting in the significant enhancement of saturated polarization ( P s ) as well as EC performance [e.g., adiabatic temperature change (Δ T ) and isothermal entropy change (Δ S )]. Under the same conditions (i.e., 333 K and 70 kV cm -1 ), the Δ T of 5.7 mol % Li 2 CO 3 -doped BZT is 1.37 K, which is larger than that of the pure BZT ceramics (0.61 K). Consequently, in cooperation with the great improvement of electric field breakdown strength ( E b ) from 70 to 150 kV cm -1 , 5.7 mol % Li 2 CO 3 -doped BZT achieved a large Δ T of 2.26 K at a temperature of 333 K, which is a competitive performance in the field of electrocaloric effect (ECE). This work provides a simple but effective approach to designing high-performance electrocaloric materials for next-generation refrigeration.

Antiferroelectric materials are promising to be used for power capacitive devices. To improve the energy storage performance, solid-solution and defect engineering are widely used to suppress the long-range order by introducing local heterogeneities. However, both methods generally deteriorate either the maximum polarization or breakdown electric field due to damaged intrinsic polarization or increased leakage. Here, we show that forming defect-dipole clusters by A-B site acceptor-donor co-doping in antiferroelectrics can comprehensively enhance the energy storage performance. We took the La-Mn co-doped (Pb 0.9 Ba 0.04 La 0.04 )(Zr 0.65 Sn 0.3 Ti 0.05 )O 3 (PBLZST) as an example. For co-doping with unequal amounts, high dielectric loss, impurity phase, and decreased polarization were observed. By contrast, La and Mn in an equal amount of co-doping can significantly improve the overall energy storage performance. An over 48% increasement in both the maximum polarization (62.7 μC/cm 2 ) and breakdown electric field (242.6 kV/cm) was obtained in 1 mol % La and 1 mol % Mn equally co-doped PBLZST, followed by a nearly two-time enhancement in W rec (6.52 J/cm 3 ) compared with that of the pure matrix. Moreover, a high energy storage efficiency of 86.3% with an enhanced temperature stability over a wide temperature range can be achieved. The defect-dipole clusters associated with charge-compensated co-doping are suggested to contribute to an enhanced dielectric permittivity, linear polarization behavior, and maximum polarization strength compared with that of the unequal co-doping cases. The defect-dipole clusters are suggested to couple with the host, leading to a high energy storage performance. The proposed strategy is believed to be applicable to modify the energy storage behavior of antiferroelectrics.