Thermodynamic consistent transport theory of Li-Ion batteries
- We will present a rigorous derivation of the equations and interface conditions for ion, charge and heat transport in Li-ion insertion batteries. The derivation is based exclusively on universally accepted principles of nonequilibrium thermodynamics and the assumption of a one step intercalation reaction at the interface of electrolyte and active particles. Without loss of generality the transport in the active particle is assumed to be isotropic. The electrolyte is described as a fully dissociated salt in a neutral solvent. The presented theory is valid for transport on a spatial scale for which local charge neutrality holds i.e. beyond the scale of the diffuse double layer. Charge neutrality is explicitely used to determine the correct set of thermodynamically independent variables. The theory guarantees strictly positive entropy production. The various contributions to the Peltier coeficients for the interface between the active particles and the electrolyte as well as the contributions to the heat of mixing are obtained as a result of the theory.