Colossal Barocaloric Effects with Ultralow Hysteresis in Two-Dimensional Metal–Halide Perovskites

Nearly 4,400 TWh of electricity—20% of the total consumed in the world—is used each year by refrigerators, air conditioners, and heat pumps for cooling. In addition to the 2.3 Gt of carbon dioxide emitted during the generation of this electricity, the vapor-compression-based devices that provided the bulk of this cooling emitted fluorocarbon refrigerants with a global warming potential equivalent to 1.5 Gt of carbon dioxide into the atmosphere. With population and economic growth expected to dramatically increase over the next several decades, the development of alternative cooling technologies with improved efficiency and reduced emissions will be critical to meeting global cooling needs in a more sustainable fashion. Barocaloric materials, which undergo thermal changes in response to applied hydrostatic pressure, offer the potential for solid-state cooling with high energy efficiency and zero direct emissions, as well as faster start-up times, quieter operation, greater amenability to miniaturization, and better recyclability than conventional vapor-compression systems. Efficient barocaloric cooling requires materials that undergo reversible phase transitions with large entropy changes, high sensitivity to hydrostatic pressure, and minimal hysteresis, the combination of which has been challenging to achieve in existing barocaloric materials. Here, we report a new mechanism for achieving colossal barocaloric effects near ambient temperature that exploits the large volume and conformational entropy changes of hydrocarbon chain-melting transitions within two-dimensional metal–halide perovskites. Significantly, we show how the confined nature of these order–disorder phase transitions and the synthetic tunability of layered perovskites can be leveraged to reduce phase transition hysteresis through careful control over the inorganic–organic interface. The combination of ultralow hysteresis (< 1.5 K) and high barocaloric coefficients (> 20 K/kbar) leads to large reversible isothermal entropy changes (> 200 J/kg•K) at record-low pressures (< 300 bar). We anticipate that these results will help facilitate the development of barocaloric cooling technologies and further inspire new materials and mechanisms for efficient solid-state cooling.