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

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 Cu₇(Te_0.74Se_0.26)₄ nanotubes with crystalline-amorphous heterointerfaces and anionic doping are delicately synthesized starting from the telluride selenium precursor. The Cu₇(Te_0.74Se_0.26)₄ nanotubes showcase multifarious advantages including high electrical conductivity, strong Zn²⁺ adsorption ability, fast ion diffusion, robust structural stability, and relatively low operating voltage. Consequently, the Cu₇(Te_0.74Se_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 Cu₇Te₄-based counterparts. More importantly, a Cu₇(Te_0.74Se_0.26)₄//CNT@MnO₂ full battery is successfully fabricated and demonstrates satisfactory electrochemical performance. Additionally, the conversion-type mechanism of the Cu₇(Te_0.74Se_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 Zn²⁺ adsorption energy, and reduce the energy barrier for Zn²⁺ 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.