Creating New Battery Configuration Associated with the Functions of Primary and Rechargeable Lithium Metal Batteries

Abstract Although the primary lithium/fluorinated graphite battery has a high energy density of 3725 Wh kg⁻¹, its complete irreversibility based on a conversion reaction between Li and fluorinated graphite hampers wide applications in rechargeable systems. Here, a new rechargeable three‐electrode battery configuration involving lithium, fluorinated graphite, and sulfur electrodes is developed, in which the initial middle‐fluorinated graphite cathode can be electrochemically transformed into a hybrid lithium anode, showing a low overpotential (12 mV), long cycle life (2000 h) and good deep stripping/plating features. This rechargeable battery delivers a high gravimetric energy density of 507.7 Wh kg⁻¹ on the basis of the total mass of the three‐electrode materials. Moreover, the excessive consumption of lithium in the system can be in situ replenished, further lengthening the lifespan.