A surface science approach to cathode/electrolyte interfaces in Li-ion batteries: Contact properties, charge transfer and reactions

Reactions and charge transfer at cathode/electrolyte interfaces affect the performance and the stability of Li-ion cells. Corrosion of active electrode material and decomposition of electrolyte are intimately coupled to charge transfer reactions at the electrode/electrolyte interfaces, which in turn depend on energy barriers for electrons and ions. Principally, energy barriers arise from energy level alignment at the interface and space charge layers near the interface, caused by changes of inner electric (Galvani) potential due to interfacial dipoles and concentration profiles of electronic and ionic charge carriers.In this contribution, we introduce our surface science oriented approach using photoemission (XPS, UPS) to investigate cathode/electrolyte interfaces in Li-ion batteries. After an overview of the processes at cathode/electrolyte interfaces as well as currently employed analysis methods, we present the fundamentals of contact potential formation and energy level alignment (electrons and ions) at interfaces and their analysis with photoemission. Subsequently, we demonstrate how interface analysis can be employed in Li-ion battery research, yielding new and valuable insights, and discuss future benefits.