Carbon Nanotubes Coupled with Metal Ion Diffusion Layers Stabilize Oxide Conversion Reactions in High-Voltage Lithium-Ion Batteries

Creating new architectures combined with super diverse materials for achieving more excellent performances has attracted great attention recently. Herein, we introduce a novel dual metal (oxide) microsphere reinforced by vertically aligned carbon nanotubes (CNTs) and covered with a titanium oxide metal ion-transfer diffusion layer. The CNTs penetrate the oxide particles and buffer structural volume change while enhancing electrical conductivity. Meanwhile, the external TiO₂–C shell serves as a transport pathway for mobile metal ions (e.g., Li⁺) and acts as a protective layer for the inner oxides by reducing the electrolyte/metal oxide interfacial area and minimizing side reactions. The proposed design is shown to significantly improve the stability and Coulombic efficiency (CE) of metal (oxide) anodes. For example, the as-prepared MnO–CNTs@TiO₂–C microsphere demonstrates an extremely high capacity of 967 mA h g^–1 after 200 cycles, where a CE as high as 99% is maintained. Even at a harsh rate of 5 A g^–1 (ca. 5 C), a capacity of 389 mA h g^–1 can be maintained for thousands of cycles. The proposed oxide anode design was combined with a nickel-rich cathode to make a full-cell battery that works at high voltage and exhibits impressive stability and life span.