Visualization of Si Anode Reactions in Coin-Type Cells via Operando Scanning Electron Microscopy

Understanding the electrochemical behavior and controlling the morphological variations of electrodes are critical for the design of high-capacity batteries. In this article, we describe a newly established operando scanning electron microscopy (SEM) to visualize the battery reactions in a modified coin cell, which allowed the simultaneous collection of electrochemical data and time-resolved images. The investigated silicon (Si)-polyimide-binder electrode exhibited a high capacity (∼1500 mAh g^-1) and a desirable cyclability. Operando SEM revealed that the morphology of the Si anode drastically changed and cracks formed on the electrode because of the lithiation-induced volume expansion of the Si particles during the first charge process. Interestingly, the thickness variation in the Si composite layer was moderated in subsequent cycles. This strongly suggested that cracking caused by the breakage of the stiff binder alleviated the internal stress experienced by Si. On the basis of this finding by the operando SEM technique, patterned Si electrodes with controlled spacing were successfully fabricated, and their improved performance was confirmed.