Giant Electrocaloric Effect and Ultrahigh Refrigeration Efficiency in Antiferroelectric Ceramics by Morphotropic Phase Boundary Design

Electrocaloric effect (ECE) in ferroelectric (FE)/antiferroelectric (AFE) materials offers a promising high-efficient and zero-emission solid-state cooling technology, whose materials design is usually focused on the morphotropic phase boundary (MPB) between two FE phases. This work constructs an MPB between an orthorhombic AFE and a rhombohedral FE phase in Pb_0.97-xBa_xLa_0.02Zr_0.95Ti_0.05O₃ (PBLZT100x, x = 0-0.08) ceramics and achieves a superior ECE performance. An unprecedented high electrocaloric strength of 1.52 K·mm/kV and an ultrahigh refrigeration efficiency (coefficient of performance = 16) are obtained in PBLZT4, in the MPB near AFE end. Moreover, a large negative ECE, with the highest strength up to -0.41 K·mm/kV, is also realized due to the electric field-induced AFE-FE transition. The coexistence of giant positive and negative ECEs at adjacent temperatures can further improve the cooling capacity (∼17%) of solid-state refrigeration in a well-designed cooling cycle. This work provides a brand new materials design strategy to achieve giant positive and negative ECEs simultaneously and a novel cooling cycle to efficiently utilize the two effects.