Dynamic Li ⁺ Respiration Effect Enables Cascade Conversion of Lithium Polysulfides for Li–S Batteries

High-energy-density lithium-sulfur batteries exhibit obvious kinetics differences involving multistep reactions, making it hard to realize constantly high-efficient polysulfide conversion during the full charging/discharging Herein, we propose a concept of Li⁺-respiration-effect-induced cascade catalysis through taking full advantage of dynamic active sites from in situ potential-modulated TiNb₂O₇. The Li⁺ respiration effect activates the lattice O atom and regulates the antibonding orbitals filling, triggering an electrochemical-dominated switchable catalytic for sequential conversion of intermediates. As a result, the Li-S cell displays a good cycling stability and wide-temperature ability from -30 to +60 °C. A flexible pouch cell maintains a capacity retention of 94.6% after 120 cycles. Our discovery provides a fire-new perspective in electrochemically reconstructed catalysis for wide-temperature-tolerant Li - S batteries.