Nano‐Heterostructured TiO ₂ ‐TiO‐TiN/MoO _3‐x ‐Mo ₂ N Composite LIB Anode With Enhanced Li

ABSTRACT

To meet the growing demand for high‐capacity and safe anode materials for lithium‐ion batteries (LIBs), we report a low‐cost, scalable strategy to fabricate a nano‐heterostructured TiO ₂ ‐TiO‐TiN/MoO _3‐x ‐Mo ₂ N (TTT/MM) composite film directly on titanium substrates. By combining glycine‐assisted anodization with cathodic deposition in a nitric‐based Mo ₇ O ₂₄ ⁶⁻ electrolyte, Mo‐containing species are incorporated into the nanoporous TTT film. The resulting binder‐ and additive‐free, fully electrochemically active film delivers a high areal discharge capacity of 2639.0 µAh cm ⁻² during charge/discharge cycling, nearly seven times higher than that of the pristine TTT matrix. Charge‐transfer resistance is reduced to only 20% of that of the original matrix, and even at a high current density of 1000 µA cm ⁻² , the film retains an areal capacity above 1000 µAh cm ⁻² with 59.1% high‐rate retention. These performance enhancements originate from the synergistic effects of glycine‐enabled high‐current rapid growth, which promotes thicker and more uniform TTT film formation, together with the introduction of high‐capacity Mo‐containing species and defect‐assisted charge transport. This work demonstrates that TiO ₂ ‐TiO‐TiN/MoO _3‐x ‐Mo ₂ N is a highly promising LIB anode, combining high performance with scalable, low‐cost fabrication for next‐generation energy storage applications.