Unusual Magnetocaloric Effect Triggered by Spin Reorientation

Abstract Advancements and utilization of magnetic refrigeration technology hinge on the ongoing enhancement and optimization of magnetic refrigeration material properties. Nevertheless, the intricacy of the magnetocaloric effect (MCE) mechanism has emerged as a bottleneck, constraining the progress and refinement of magnetic refrigeration materials. In this study, a classic magnetic system is chosen to investigate the mechanism of MCE across four different scales–macroscopic magnetism, micrometer‐scale magnetic domains, atomic magnetic moments, and electronic structure. It simultaneously exhibits two inverse MCEs and one direct MCE, with a working temperature span as wide as 125 K (most are <50 K) for the direct MCE. The measurements of the vibrating sample magnetometer, in situ Lorentz electron microscopy and variable‐temperature neutron powder diffraction directly reveal that the complex magnetic entropy changes arise from the magnetic domain wall pinning, the instability of Ho magnetic moments, and the spin rotation. First‐principles calculations elucidate the crucial role of strong hybridization between localized Ho and itinerant Co electrons in the spin reorientation of HoCo 4 Al. This study contributes significantly to comprehending the induction mechanism of the MCE and holds vital reference value for exploring new magnetic refrigeration materials and enhancing MCE performance.