Defect Promoted Capacity and Durability of N‐MnO_2–<i>_x</i> Branch Arrays via Low‐Temperature NH₃ Treatment for Advanced Aqueous Zinc Ion Batteries

Abstract

Defect engineering (doping and vacancy) has emerged as a positive strategy to boost the intrinsic electrochemical reactivity and structural stability of MnO₂ -based cathodes of rechargeable aqueous zinc ion batteries (RAZIBs). Currently, there is no report on the nonmetal element doped MnO₂ cathode with concomitant oxygen vacancies, because of its low thermal stability with easy phase transformation from MnO₂ to Mn₃ O₄ (≥300 °C). Herein, for the first time, novel N-doped MnO_2- _x (N-MnO_2- _x ) branch arrays with abundant oxygen vacancies fabricated by a facile low-temperature (200 °C) NH₃ treatment technology are reported. Meanwhile, to further enhance the high-rate capability, highly conductive TiC/C nanorods are used as the core support for a N-MnO_2- _x branch, forming high-quality N-MnO_2- _x @TiC/C core/branch arrays. The introduced N dopants and oxygen vacancies in MnO₂ are demonstrated by synchrotron radiation technology. By virtue of an integrated conductive framework, enhanced electron density, and increased surface capacitive contribution, the designed N-MnO_2- _x @TiC/C arrays are endowed with faster reaction kinetics, higher capacity (285 mAh g^-1 at 0.2 A g^-1 ) and better long-term cycles (85.7% retention after 1000 cycles at 1 A g^-1 ) than other MnO₂ -based counterparts (55.6%). The low-temperature defect engineering sheds light on construction of advanced cathodes for aqueous RAZIBs.