A Carboxyl-Modified Polyaniline Cathode for High-Performance Aqueous Zinc-Ion Batteries

Inherent conductivity and high redox activity endow polyaniline (PANI) with great potential to serve as a cathode material for aqueous zinc-ion batteries. However, compared with traditional strongly acidic electrolytes (pH < 1), its electrochemical performances are moderated in weakly acidic zinc salt electrolytes (pH > 3) because of spontaneous deprotonation. Herein, a carboxyl-modified PANI was designed and synthesized by introducing carboxyl groups at the para-position of the terminal benzene rings within the polymer chains. In this conjugated system, the electron density in the polymer chains was redistributed with a higher one around the substituent due to the electron-withdrawing effect of carboxyl groups and meanwhile carboxyl groups characterized by a proton donor render PANI achieve a proton-involved electrochemical reaction. Consequently, the carboxyl-modified PANI cathode, in a Zn//PANI cell, delivers an impressive specific capacity of 226 mAh g−1 along with excellent rata capability and cycling stability. This work presented some new insights into the molecule structure design of PANI-based polymers applied in advanced aqueous batteries.