An anode-free Li metal cell with replenishable Li designed for long cycle life

Abstract Pit corrosion of Li during stripping is an important factor responsible for poor Li cycling efficiency, a metric that determines its cycling life. When excess Li is present, it has been observed that Li tends to strip in a non-uniform fashion, forming pits that extend well past the theoretical Li depth that inevitably lead to the formation of electronically isolated “dead” Li particles. In this work, a novel cell with replenishable Li is shown to inherently mitigate the formation of this “dead” Li, as a direct result of a design in which the intrinsically more homogenous stripping behavior of anode-free cells are combined with a replenishable limited Li reservoir. These novel cells (Li|Cu||LiFePO4) exhibit 25% and 34% higher cumulative capacities than the conventional cells (Cu|Li||LiFePO4) in carbonate and ether electrolytes, respectively, enabling a significant increase in cycle life without impacting energy density. This improvement strategy represents a new direction in Li metal battery improvement, in which improved cycling can be achieved regardless of electrolyte chemistry.