Template‐Assisted Calcination to Construct Ti 2 Nb 14 O 39 Penetrating Ion Channels: Solving the Synergistic Problem of Electron Conduction/Structural Stability

Titanium niobium oxide is a promising anode candidate for lithium‐ion batteries due to its high working potential, stability, and theoretical capacity. However, the difficult synergistic regulation of electronic conduction and structural stability, a critical challenge, combined with poor electronic/ionic transport kinetics, restricts its commercial application. Herein, a solvothermal‐F127 template synergistic strategy was used to construct hierarchical porous microspheres assembled from Ti 2 Nb 14 O 39 nanoparticles. This structure provides a high specific surface area and short ion diffusion paths, while micrometer‐scale mechanical stability suppresses nanoparticle agglomeration. The F127‐induced three‐dimensional network enhances ion transport by 1–2 orders of magnitude. Nanoparticle contacts form an electron transport framework, and oxygen‐vacancy‐induced polaron transitions create fast electron channels, overcoming the limitations of traditional Ti‐Nb oxides in conductivity and ion kinetics. The optimised material delivers an initial charge capacity of 299.76 mAh g −1 (0.1C), maintains 174.68 mAh g −1 at 40C, and exhibits 85.33% capacity retention after 200 cycles (5C). This work effectively addresses the simultaneous regulation of electronic conduction and structural stability in Nb‐based materials, providing a universal design approach for high‐power energy storage devices.