Large thermal hysteresis in the (Mn,Fe)2(P,Si) system hinders an efficient heat exchange and thus limits the magnetocaloric applications. Substitution of manganese by vanadium in the Mn1-x1Vx1Fe0.95P0.593Si0.33B0.077 and Mn1-x2Vx2Fe0.95P0.563Si0.36B0.077 compounds enable a significant reduction in the thermal hysteresis without losing the giant magnetocaloric effect. For the composition closest to the critical one, where first-order crossovers to second-order phase transition in the series of x2 = 0.02, Mn0.98V0.02Fe0.95P0.563Si0.36B0.077 exhibits a thermal hysteresis that is reduced from 1.5 to 0.5 K by 67%, yielding an adiabatic temperature change of 2.3 K and magnetic entropy change of 5.6 J/kgK for an applied field of 1 T, which demonstrates its potential for highly efficient magnetic heat pumps utilizing low-cost permanent magnets.

Simultaneous operando Nuclear Forward Scattering and transmission X-ray diffraction and ⁵⁷Fe Mössbauer spectroscopy measurements were carried out in order to investigate the electrochemical mechanism of NaFeO₂ vs. Na metal using a specifically designed in situ cell. The obtained data were analysed using an alternative and innovative data analysis approach based on chemometric tools such as Principal Component Analysis (PCA) and Multivariate Curve Resolution - Alternating Least Squares (MCR-ALS). This approach, which allows the unbiased extraction of all possible information from the operando data, enabled the stepwise reconstruction of the independent “real” components permitting the description of the desodiation mechanism of NaFeO₂. This wealth of information allows a clear description of the electrochemical reaction at the redox-active iron centres, and thus an improved comprehension of the cycling mechanisms of this material vs. sodium.