Synchronous Engineering of Crystalline‐Amorphous Heterointerfaces and Anionic Doping in Copper Telluride Nanotubes Toward High‐Performance Rocking‐Chair Aqueous Zn‐Ion Batteries

Abstract Rocking‐chair aqueous Zn‐ion batteries (AZIBs) hold great promise for applications in large‐scale energy storage systems. Unfortunately, the development of advanced anode materials still remains a formidable challenge. Herein, for the first time, unique Cu ₇ (Te _0.74 Se _0.26 ) ₄ nanotubes with crystalline‐amorphous heterointerfaces and anionic doping are delicately synthesized starting from the telluride selenium precursor. The Cu ₇ (Te _0.74 Se _0.26 ) ₄ nanotubes showcase multifarious advantages including high electrical conductivity, strong Zn ²⁺ adsorption ability, fast ion diffusion, robust structural stability, and relatively low operating voltage. Consequently, the Cu ₇ (Te _0.74 Se _0.26 ) ₄ anode exhibits remarkable specific discharge capacity, outstanding rate capability and decent long‐term cycling stability (≈86.6% capacity retention over 15 000 cycles at 5 A g ⁻¹ ), outperforming the other Cu ₇ Te ₄ ‐based counterparts. More importantly, a Cu ₇ (Te _0.74 Se _0.26 ) ₄ //CNT@MnO ₂ full battery is successfully fabricated and demonstrates satisfactory electrochemical performance. Additionally, the conversion‐type mechanism of the Cu ₇ (Te _0.74 Se _0.26 ) ₄ anode is further comprehensively investigated by a series of ex situ characterization measurements. Furthermore, theoretical calculations reveal that the synchronous engineering of crystalline‐amorphous heterointerfaces alongside Se doping can effectively enhance the electrical conductivity, improve the Zn ²⁺ adsorption energy, and reduce the energy barrier for Zn ²⁺ migration. This contribution provides an innovative methodology for designing new‐type anode materials through interface engineering and anionic doping simultaneously for high‐performance rocking‐chair AZIBs.