In-situ determination of onset lithium plating for safe Li-ion batteries

Lithium plating in working batteries has attracted wide attention in the exploration of safe energy storage. Establishing an effective and rapid early-warning method is strongly considered but quite challenging since lithium plating behavior is determined by diverse factors. In this contribution, we present a non-destructive electrochemical detection method based on transient state analysis and three-electrode cell configuration. Through dividing the iR drop value by the current density, the as-obtained impedance quantity (Ri) can serve as a descriptor to describe the change of electrochemical reaction impedance on the graphite anode. The onset of lithium plating can be identified from the sharp drop of Ri. Once the dendritic plated lithium occurs, the extra electrochemical reactions at the lithium interfaces leads to growing active area and reduced surface resistance of the anode. We proposed a protocol to operate the batteries under the limited capacity, which renders the cell with 98.2% capacity retention after 1000 cycles without lithium plating. The early-warning method has also been validated in in-situ optical microscopy batteries and practical pouch cells, providing a general but effective method for online lithium plating detection towards safe batteries.