Dissipation losses limiting first-order phase transition materials in cryogenic caloric cooling: A case study on all-d-metal Ni(-Co)-Mn-Ti Heusler alloys

TL;DR

This study investigates dissipation losses in Ni-Co-Mn-Ti Heusler alloys, revealing how entropy compensation and hysteresis at cryogenic temperatures limit their effectiveness in solid-state refrigeration applications.

Contribution

It provides a comprehensive analysis of transition entropy change and dissipation effects in Ni-Co-Mn-Ti alloys, highlighting universal limitations for first-order caloric materials at cryogenic temperatures.

Findings

Structural entropy change is about 65 J/(kg·K).

Hysteresis and dissipation increase at cryogenic temperatures.

Sign change and irreversibility in adiabatic temperature change.

Abstract

Ni-Mn-based Heusler alloys, in particular all-d-metal Ni(-Co)-Mn-Ti, are highly promising materials for energy-efficient solid-state refrigeration as large multicaloric effects can be achieved across their magnetostructural martensitic transformation. However, no comprehensive study on the crucially important transition entropy change $\Delta s_t$ exists so far for Ni(-Co)-Mn-Ti. Here, we present a systematic study analyzing the composition and temperature dependence of $\Delta s_t$. Our results reveal a substantial structural entropy change contribution of approximately 65 J(kgK)$^{-1}$, which is compensated at lower temperatures by an increasingly negative entropy change associated with the magnetic subsystem. This leads to compensation temperatures $T_{comp}$ of 75 K and 300 K in Ni$_{35}$Co$_{15}$Mn$_{50-y}$Ti$_{y}$ and Ni$_{33}$Co$_{17}$Mn$_{50-y}$Ti$_{y}$, respectively, below which the martensitic transformations are arrested. In addition, we simultaneously measured the responses of the magnetic, structural and electronic subsystems to the temperature- and field-induced martensitic transformation near $T_{comp}$, showing an abnormal increase of hysteresis and consequently dissipation energy at cryogenic temperatures. Simultaneous measurements of magnetization and adiabatic temperature change $\Delta T_{ad}$ in pulsed magnetic fields reveal a change in sign of $\Delta T_{ad}$ and a substantial positive and irreversible $\Delta T_{ad}$ up to 15 K at 15 K as a consequence of increased dissipation losses and decreased heat capacity. Most importantly, this phenomenon is universal, it applies to any first-order material with non-negligible hysteresis and any stimulus, effectively limiting the utilization of their caloric effects for gas liquefaction at cryogenic temperatures.