Promoting Ge Alloying Reaction via Heterostructure Engineering for High Efficient and Ultra‐Stable Sodium‐Ion Storage

Abstract Germanium (Ge)‐based materials have been considered as potential anode materials for sodium‐ion batteries owing to their high theoretical specific capacity. However, the poor conductivity and Na+ diffusivity of Ge‐based materials result in retardant ion/electron transportation and insufficient sodium storage efficiency, leading to sluggish reaction kinetics. To intrinsically maximize the sodium storage capability of Ge, the nitrogen doped carbon‐coated Cu3Ge/Ge heterostructure material (Cu3Ge/Ge@N‐C) is developed for enhanced sodium storage. The pod‐like structure of Cu3Ge/Ge@N‐C exposes numerous active surface to shorten ion transportation pathway while the uniform encapsulation of carbon shell improves the electron transportation, leading to enhanced reaction kinetics. Theoretical calculation reveals that Cu3Ge/Ge heterostructure can offer decent electron conduction and lower the Na+ diffusion barrier, which further promotes Ge alloying reaction and improves its sodium storage capability close to its theoretical value. In addition, the uniform encapsulation of nitrogen‐doped carbon on Cu3Ge/Ge heterostructure material efficiently alleviates its volume expansion and prevents its decomposition, further ensuring its structural integrity upon cycling. Attributed to these unique superiorities, the as‐prepared Cu3Ge/Ge@N‐C electrode demonstrates admirable discharge capacity, outstanding rate capability and prolonged cycle lifespan (178 mAh g−1 at 4.0 A g−1 after 4000 cycles).