Recent Progress on In Situ/Operando Characterization of Rechargeable Alkali Ion Batteries.

The specific chemical and physical evolutions of electrode materials under operating conditions should be understood to optimize their electrochemical performances. The in-situ/operando techniques including Raman spectrum, transmission electron microscope, X-ray diffraction, X-ray absorption spectrum, and magnetization are powerful tools, which can provide the real-time surficial/interfacial changes of electrodes, the transformation of crystal lattice structures, the adjustment of electronic states and even the influence of magnetic properties under operating conditions. In this Review, the advantages and limitations of these in-situ/operando techniques in investigating the inner energy storage mechanisms of various type electrode materials are analyzed. The representative research results such as the ion dependent storage mechanism, step-alloying processes and space charge storage theory are highlighted. In addition, the challenges and opportunities of in-situ/operando characterizations are proposed as well.