Correlation between the equilibrium and transport properties of intercalation systems

Electrochemically driven first-order phase transitions caused by elastic responses of ion-insertion electrodes under external kinetic control

“…The application of the continuum elasticity model to ion insertion into host electrodes (characterized by an intercalation level X: 0 < X < 1) introduces three major composition-dependent characteristics, such as the loading stress, r(X), the strain in the electrode bulk, e(X), and the self-stress ke(X), as a reaction of the host to the guest ions insertion [7,8]. k is a dimensionless composition-independent elastic constant.…”

“…This effect must suggest the presence of additional terms in the chemical potential of guest ions in the host matrix (compared to the conventional term proportional to the ions concentration). Recently, two approaches, based on (i) the continuum theory of elasticity with the concentration-dependent stress and strain fields [7,8] and (ii) a combination of the standard statistical mechanics and the information theory [9], led to the same conclusion: the expression for the chemical potential of ion in solids should include terms related not only to the concentration-dependent stress and strain themselves, but also to their derivatives with respect to the ion concentration. This theory was successfully used to explain the host distortion during Li-ion insertion into TiS 2 and WO 3 , including the thermodynamic consequences of this distortion [7,8,10].…”

“…An important feature of the elastic model proposed in [1,2,6] is that as the net strain in the electrode becomes zero (e.g. in the case of the perfectly clamped electrode), the elastic dipole interactions do not disappear [7].…”

“…The approach used in Refs. [7][8][9] introduced three major composition-dependent elastic characteristics, such as the loading stress, r(X), the strain in the electrode bulk, e(X), and the self-stress ke(X) (k is the composition-independent elastic constant) as a reaction of the host to the guest ions insertion.…”

A life in Science: In memory of Jean-Pierre Badiali

“…For the first time, they took into account the fact that a change of the volume of the host material may have a strong effect on the insertion mechanism. Employing the lattice gas model combined with the linear elasticity theory, they argued that major features of intercalation isotherms can be well understood in terms of the link between configurational and structural transitions [42][43][44]. The developed theory provides a quantitative description of different insertion processes and was used for the interpretation of the experiments in different experimental groups [45][46][47].…”