X-ray
photoemission electron microscopy (XPEEM), with its excellent
spatial resolution, is a well-suited technique for elucidating the
complex electrode–electrolyte interface reactions in Li-ion
batteries. It provides element-specific contrast images that allows
the study of the surface morphology and the identification of the
various components of the composite electrode. It also enables the
acquisition of local X-ray absorption spectra (XAS) on single particles
of the electrode, such as the C and O K-edges to track the stability
of carbonate-based electrolytes, F K-edge to study the electrolyte
salt and binder stability, and the transition metal L-edges to gain
insights into the oxidation/reduction processes of positive and negative
active materials. Here we discuss the optimal measurement conditions
for XPEEM studies of Li-ion battery systems, including (i) electrode
preparation through mechanical pressing to reduce surface roughness
for improved spatial resolution; (ii) corrections of the XAS spectra
at the C K-edge to remove the carbon signal contribution originating
from the X-ray optics; and (iii) procedures for minimizing the effect
of beam damage. Examples from our recent work are provided to demonstrate
the strength of XPEEM to solve challenging interface reaction mechanisms
via post mortem measurements. Finally, we present
a first XPEEM cell dedicated to operando/in situ experiments
in all-solid-state batteries. Representative measurements were carried
out on a graphite electrode cycled with LiI-incorporated sulfide-based
electrolyte. This measurement demonstrates the strong competitive
reactions between the lithiated graphite surface and the Li2O formation caused by the reaction of the intercalated lithium with
the residual oxygen in the vacuum chamber. Moreover, we show the versatility
of the operando XPEEM cell to investigate other active materials,
for example, Li4Ti5O12.