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.
In order to improve the design of Li ion batteries the complex interplay of various physical phenomena in the active particles of the electrodes and in the electrolyte has to be balanced. The separate transport phenomena in the electrolyte and in the active particle as well as their coupling due to the electrochemical reactions at the interfaces between the electrode particles and the electrolyte will inuence the performance and the lifetime of a battery. Any modeling of the complex phenomena during the usage of a battery has therefore to be based on sound physical and chemical principles in order to allow for reliable predictions for the response of the battery to changing load conditions. We will present a modeling approach for the transport processes in the electrolyte and the electrodesbased on non-equilibrium thermodynamics and transport theory. The assumption of local charge neutrality, which is known to be valid in concentrated electrolytes, is explicitly used to identify the independent thermodynamic variables and uxes. The theory guarantees strictly positive entropy production. Dierences to other theories will be discussed.