Evidence of Quasi‐Na Metallic Clusters in Sodium Ion Batteries through In Situ X‐Ray Diffraction

Abstract Carbonaceous materials have been considered the most promising anode in sodium‐ion batteries (SIBs) due to their low cost, good electrical conductivity, and structural stability. The main challenge of carbonaceous anodes prior to their commercialization is low initial coulomb efficiencies, derived from a lack of an efficient technique to reveal a fundamental comprehension of sodium storage mechanisms. Here, the direct observation of quasi‐Na metallic clusters in carbonaceous anodes during cycling through in situ XRD is reported. By means of such a technique, a strong self‐adsorption behavior forming quasi‐Na metallic clusters is detected within a rationally designed highly defective ultrathin carbon nanosheets (HDCS) anode. Such a self‐adsorption and crystalline system transformation mechanism in HDCS brings capacity retention about 100% after 1000 cycles at 1 A g⁻¹. This work provides a new principle for designing high‐performance carbon anodes for SIBs.