As a promising alternative
to the market-leading lithium-ion batteries,
low-cost sodium-ion batteries (SIBs) are attractive for applications
such as large-scale electrical energy storage systems. The energy
density, cycling life, and rate performance of SIBs are fundamentally
dependent on dynamic physiochemical reactions, structural change,
and morphological evolution. Therefore, it is essential to holistically
understand SIBs reaction processes, degradation mechanisms, and thermal/mechanical
behaviors in complex working environments. The recent developments
of advanced in situ and operando characterization
enable the establishment of the structure–processing–property–performance
relationship in SIBs under operating conditions. This Review summarizes
significant recent progress in SIBs exploiting in situ and operando techniques based on X-ray and electron analyses at
different time and length scales. Through the combination of spectroscopy,
imaging, and diffraction, local and global changes in SIBs can be
elucidated for improving materials design. The fundamental principles
and state-of-the-art capabilities of different techniques are presented,
followed by elaborative discussions of major challenges and perspectives.
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