Thermodynamically consistent modeling of elementary electrochemistry in lithium-ion batteries

This paper is particularly concerned with the elementary reactions and transport processes that are responsible for Li-ion battery performance The model generally follows the widely practiced approach developed by Newman and co-workers (e g. Doyle et al J Electrochem Soc 140 (1993) 1526 [1]) However there are significant departures especially in modeling electrochemical charge transfer The present approach introduces systems of microscopically reversible reactions including both heterogeneous thermal reactions and electrochemical charge-transfer reactions All reaction rates are evaluated in elementary form providing a powerful alternative to a Butler-Volmer formalism for the charge-transfer reactions The paper is particularly concerned with the influence of non-ideal thermodynamics for evaluating reversible potentials as well as charge-transfer rates The theory and modeling approach establishes a framework for extending chemistry models to incorporate detailed reaction mechanisms that represent multiple competitive reaction pathways (C) 2010 Elsevier Ltd All rights reserved