Polyacrylic acid assisted synthesis of free-standing MnO2/CNTs cathode for Zinc-ion batteries

Rechargeable aqueous zinc-ion batteries (ZIBs) have attracted significant attention due to the distinguishing characteristics of zinc metal, including its low price, abundance in earth, safety and high theoretical specific capacity of 820 mAh g-1. Manganese dioxide (MnO2) is a promising cathode for ZIBs due to high theoretical specific capacity, high discharge voltage plateau, cost-effectiveness and nontoxicity. However, the low electronic conductivity and volumetric changes during electrochemical cycling hinder its practical utilization. Herein, we demonstrate a polyacrylic acid (PAA)-assisted assembling strategy to fabricate freestanding and flexible MnO2/carbon nanotube/PAA (MnO2/CNT/PAA) cathodes for ZIBs. PAA plays an important role in providing excellent mechanical properties to the free-standing electrode. Moreover, the presence of CNT forms an electron conductive network, and the porous structure of MnO2/CNT/PAA electrode accommodates the volumetric variations of MnO2 during charge/discharge cycling. The as-fabricated quasi-solid-state Zn-MnO2/CNT/PAA battery delivers a high charge storage capacity of 302 mAh g-1 at 0.3 A g-1 and retains 82% of the initial capacity after 1000 charge/discharge cycles at 1.5 A g-1. The calculated volumetric energy density of Zn-MnO2/CNT/PAA battery is 8.5 mW h cm-3 (with a thickness of 0.08 cm), which is significantly higher than the reported alkali-ion batteries (1.3 mW h cm-3) and comparable to supercapacitors (6.8 mW h cm-3) and Ni-Zn batteries (7.76 mW h cm-3). The current work demonstrates that free-standing MnO2/CNT/PAA composite is a promising cathode for ZIBs.