Giant barocaloric effects in sodium hexafluorophosphate and hexafluoroarsenate

Zhang, Z.*; Hattori, Takanori   ; Song, R.*; Yu, D.*; Mole, R.*; Chen, J.*; He, L.*; Zhang, Z.*; Li, B.*

Solid-state refrigeration using barocaloric materials is environmentally friendly and highly efficient, making it a subject of global interest over the past decade. Here, we report giant barocaloric effects in sodium hexafluorophosphate (NaPF) and sodium hexafluoroarsenate (NaAsF) that both undergo a cubic-to-rhombohedral phase transition near room temperature. We have determined that the low-temperature phase structure of NaPF is a rhombohedral structure with space group R and NaAsF, i.e., F, E, and A. The phase transition temperature varies with pressure at a rate of dT/dP = 250 and 310 K/GPa for NaPF and NaAsF. The pressure-induced entropy changes of NaPF and NaAsF are determined to be around 45.2 and 35.6J kgK, respectively. The saturation driving pressure is about 40 MPa. The pressure-dependent neutron powder diffraction suggests that the barocaloric effects are related to the pressure-induced cubic-to-rhombohedral phase transitions.