Thermodynamics of Electrochemical Lithium Storage

Abstract

The thermodynamics of electrochemical lithium storage are examined by taking into account that it is the point defects that enable storage. While the Li defects are mobile, most of the other point defects have to be considered as frozen owing to the performance temperature being low compared to the melting point of the electrode materials. The defect chemistry needs to be considered to fully understand equilibrium charge/discharge curves. On this basis, single phase and multiphase storage mechanisms can be discussed in terms of theoretical storage capacity and theoretical voltage. Of paramount interest in the field of Li batteries are metastable materials, in particular nanocrystalline and amorphous materials. The thermodynamics of storage and voltage, also at interfaces, thus deserve a special treatment. The relationship between reversible cell voltage and lithium content is derived for the novel job‐sharing mechanism. With respect to the classic storage modes, thermodynamic differences for cathodes and anodes are elaborated with a special attention being paid to the search for new materials. As this contribution concentrates on the equilibrium state, current‐related phenomena (irreversible thermodynamics) are only briefly touched upon.