Oxygen-Deficient α-MnO₂ Nanotube/Graphene/N, P Codoped Porous Carbon Composite Cathode To Achieve High-Performing Zinc-Ion Batteries

Abstract

A major drawback of α-MnO2-based zinc-ion batteries (ZIBs) is the poor rate performance and short cycle life. Herein, an oxygen-deficient α-MnO2 nanotube (VO-α-MnO2)-integrated graphene (G) and N, P codoped cross-linked porous carbon nanosheet (CNPK) composite (VO-α-MnO2/CNPK/G) has been prepared for advanced ZIBs. The introduction of VO in MnO2 can decrease the value of the Gibbs free energy of Zn2+ adsorption near VO (ca. −0.73 eV) to the thermal neutral value. The thermal neutral value demonstrates that the Zn2+ adsorption/desorption process on VO-α-MnO2 is more reversible than that on α-MnO2. The as-made Zn/VO-α-MnO2 battery is able to deliver a large capacity of 305.0 mAh g–1 and high energy density up to 408.5 Wh kg–1. The good energy storage properties can be attributed to VO. Additionally, the VO-α-MnO2/CNPK/G composite possesses the structure of nanotube arrays, which results from the vertical growth of α-MnO2 nanotubes on CNPK. This unique array structure helps to realize fast ion/electron transfer and stable microstructure. The electrochemical performance of VO-α-MnO2 has been comprehensively improved by compositing with G and CNPK. The VO-α-MnO2/CNPK/G can achieve capacity up to 405.2 mAh g–1, energy density of 542.2 Wh kg–1, and long cycle life (80% capacity retention after 2000 cycles).