Toward Operando Characterization of Interphases in Batteries.

Electrode/electrolyte interfaces are the most important and least understood components of Li-ion and next-generation batteries. An improved understanding of interphases in batteries will undoubtedly lead to breakthroughs in the field. Traditionally, evaluating those interphases involves using ex situ surface sensitive and/or imaging techniques. Due to their very dynamic and reactive nature, ex situ sample manipulation is undesirable. From this point of view, operando surface sensitive techniques represent a major opportunity to push boundaries in battery development. While numerous bulk spectroscopic, scattering, and imaging techniques are well established and widely used, surface sensitive operando techniques remain challenging and, to a larger extent, restricted to the model systems. Here, we give a perspective on techniques with the potential to characterize solid/liquid interfaces in both model and realistic battery configurations. The focus is on techniques that provide chemical and structural information at length and time scales relevant for the solid electrolyte interphase (SEI) formation and evolution, while also probing representative electrode areas. We highlight the following techniques: vibrational spectroscopy, X-ray photoelectron spectroscopy (XPS), neutron and X-ray reflectometry, and grazing incidence scattering techniques. Comprehensive overviews, as well as promises and challenges, of these techniques when used operando on battery interphases are discussed in detail.