Long‐Lifespan and High‐Rate Energy Storage Enabled by Lithium‐Free Batteries with External Li Supply

Abstract Energy storage batteries are pivotal for enabling reliable integration of renewable energy systems, yet further advancements in their longevity and rate performance remain imperative. Lithium (Li)‐free cathode materials, while offering exceptional electrochemical stability, rate capability, and cost efficiency, face a critical limitation: the absence of active Li ions when paired with conventional graphite anodes. To address this challenge, a Li‐free battery design is presented that integrates a graphite|TiS 2 pouch cell architecture with a standard electrolyte modified by lithium trifluoromethanesulfinate (LiSO 2 CF 3 ). This additive serves as an in situ Li‐ion reservoir, electrochemically releasing Li ions during operation without generating deleterious residues or compromising structural integrity. The optimized cell achieves an unprecedented cycle life exceeding 14 000 cycles at a high current rate of 10C, alongside remarkable sustainability and cost‐effectiveness. This work establishes a practical pathway for deploying long‐lasting, fast‐charging Li‐free batteries in grid‐scale energy storage applications.