Ultra‐High Capacity Lithium‐Ion Batteries with Hierarchical CoO Nanowire Clusters as Binder Free Electrodes

Although transition metal oxide electrodes have large lithium storage capacity, they often suffer from low rate capability, poor cycling stability, and unclear additional capacity. In this paper, CoO nanowire clusters (NWCs) composed of ultra‐small nanoparticles (≈10 nm) directly grown on copper current collector are fabricated and evaluated as an anode of binder‐free lithium‐ion batteries, which exhibits an ultra‐high capacity and good rate capability. At a rate of 1 C (716 mA g −1 ), a reversible capacity as high as 1516.2 mA h g −1 is obtained, and even when the current density is increased to 5 C, a capacity of 1330.5 mA h g −1 could still be maintained. Importantly, the origins of the additional capacity are investigated in detail, with the results suggesting that pseudocapacitive charge and the higher‐oxidation‐state products are jointly responsible for the large additional capacity. In addition, nanoreactors for the CoO nanowires are fabricated by coating the CoO nanowires with amorphous silica shells. This hierarchical core–shell CoO@SiO 2 NWC electrode achieves an improved cycling stability without degrading the high capacity and good rate capability compared to the uncoated CoO NWCs electrode.