No abstract

This study reports the phase transformation behaviour associated with electrolytic manganese dioxide (EMD) utilized as the positive electrode active material for aqueous zinc-ion batteries. Electrochemical techniques, including galvanostatic charge–discharge and rotating ring-disk electrode measurements, and microstructural techniques, using X-ray powder diffraction, scanning electron microscopy, and transmission/scanning transmission electron microscopy, were utilized to characterize the positive electrode at different stages of discharge and charge of zinc-ion cells. The results indicate that, during discharge, a fraction of EMD undergoes a transformation to ZnMn2O4 (spinel-type) and Zn2+ is intercalated into the tunnels of the γ- and ε-MnO2 phases, forming ZnxMnO2 (tunnel-type). When a critical concentration of Mn3+ in the intercalated ZnxMnO2 species is reached, a disproportionation/dissolution reaction is triggered leading to the formation of soluble Mn2+ and hydroxide (OH–) ions; the latter precipitates as zinc hydroxide sulfate (ZHS, Zn4(OH)6(SO4)·5H2O) by combination with the ZnSO4/H2O electrolyte. During charge, Zn2+ is reversibly deintercalated from the intergrown tunneled phases (γ-/ε-ZnxMnO2), Mn2+ is redeposited as layered chalcophanite (ZnMn3O7·3H2O), and ZHS is decomposed by protons (H+) formed during the electrochemical deposition of chalcophanite.

Poly(acrylic acid) (PAA) is a promising polymer host to support alkaline electrolytes in Zn‐air batteries. Herein, precursors containing different concentrations of monomers, crosslinkers and additives such as zinc oxide in alkaline solution are polymerized to fabricate gel polymer electrolytes (GPEs) via one‐pot synthesis. The compositional effects of the GPEs on battery performance are evaluated and a more efficient cell design is demonstrated. With a vertical double air electrode configuration, ZABs using PAA‐based electrolytes show unprecedented performance including high specific energy (913 Wh kgZn−1), excellent cycling stability (at least 160 cycles at 2×10 mA cm−2) and high power density output (2×135 mW cm−2). The study represents a viable option to replace aqueous electrolytes for high performing ZABs.

Zinc-air batteries (ZABs) using gel polymer electrolytes suffer from low energy efficiency and poor cyclability. This issue is not only associated with the air electrode, as early failure of the battery is often due to the Zn electrode. Here, the cycle life of ZABs using alkaline poly(acrylic acid) (PAA-KOH) as the electrolyte is shown to vary by changing its crosslinking density. For ZABs using hydrogel electrolytes, understanding the failure mechanism and optimization of the hydrogel composition are key to achieving better utilization of the Zn electrode and battery rechargeability. In addition, the effects of crosslinker concentration on rheological properties, sol-gel fraction, ionic conductivity, and water retention ability of the hydrogel are discussed. PAA-KOH gels with lower crosslinking concentrations are weaker, but they have higher conductivity and better water retention, whereas gels with higher crosslinking concentrations affect the diffusion of zincate ions and facilitate passivation of the Zn electrode, resulting in early failure of the battery.[a] T.

No abstract