An Integrated Cell Design for Li-Free Cathodes Enables 5000-Cycle Graphite–SPAN Cells

Abstract Lithium (Li)-free cathodes represent an important class of electrode materials for Li-ion batteries, but pre-lithiation is required when they are paired with graphite anodes. Existing pre-lithiation strategies typically suffer from limited controllability and/or nonuniform lithiation, limiting the long-term stability of the cells. Here, an integrated cell design is proposed that incorporates an auxiliary Li electrode to enable precise, efficient, and thermally controlled pre-lithiation within a single cell configuration. By reconfiguring the electrical connections, the cell can be seamlessly switched between pre-lithiation and normal cycling modes. Using sulfurized polyacrylonitrile (SPAN) as a representative Li-free cathode, the (Li|Gr)||SPAN integrated cell delivers an unprecedented 5000-cycle lifespan. Moreover, the integrated design enables repeated Li replenishment during cycling, effectively restoring capacity and extending cell lifetime. The universality of this strategy is further validated with lithium titanate-based cells. This work establishes a universal integrated cell design for ultralong-life full cells with Li-free cathodes.