Rechargeable Li-metal batteries have the potential to more than double the specific energy of the state-of-the-art rechargeable Li-ion batteries, making Li-metal batteries a prime candidate for next-generation high-energy battery technology1–3. However, current Li-metal batteries suffer from fast cycle degradation compared with their Li-ion battery counterparts2,3, preventing their practical adoption. A main contributor to capacity degradation is the disconnection of Li from the electrochemical circuit, forming isolated Li4–8. Calendar ageing studies have shown that resting in the charged state promotes further reaction of active Li with the surrounding electrolyte9–12. Here we discover that calendar ageing in the discharged state improves capacity retention through isolated Li recovery, which is in contrast with the well-known phenomenon of capacity degradation observed during the charged state calendar ageing. Inactive capacity recovery is verified through observation of Coulombic efficiency greater than 100% on both Li||Cu half-cells and anode-free cells using a hybrid continuous–resting cycling protocol and with titration gas chromatography. An operando optical setup further confirms excess isolated Li reactivation as the predominant contributor to the increased capacity recovery. These insights into a previously unknown pathway for capacity recovery through discharged state resting emphasize the marked impact of cycling strategies on Li-metal battery performance.
