Entropy and Isokinetic Temperature in Fast Ion Transport

Abstract Ion transport in crystalline solids is an essential process for many electrochemical energy converters such as solid‐state batteries and fuel cells. Empirical data have shown that ion transport in crystal lattices obeys the Meyer‐Neldel Rule (MNR). For similar, closely related materials, when the material properties are changed by doping or by strain, the measured ionic conductivities showing different activation energies intersect on the Arrhenius plot, at an isokinetic temperature. Therefore, the isokinetic temperature is a critical parameter for improving the ionic conductivity. However, a comprehensive understanding of the fundamental mechanism of MNR in ion transport is lacking. Here the physical significance and applicability of MNR is discussed, that is, of activation entropy‐enthalpy compensation, in crystalline fast ionic conductors, and the methods for determining the isokinetic temperature. Lattice vibrations provide the excitation energy for the ions to overcome the activation barrier. The multi‐excitation entropy model suggests that isokinetic temperature can be tuned by modulating the excitation phonon frequency. The relationship between isokinetic temperature and isokinetic prefactor can provide information concerning conductivity mechanisms. The need to effectively determine the isokinetic temperature for accelerating the design of new fast ionic conductors with high conductivity is highlighted.