Rechargeable aqueous zinc-manganese dioxide batteries with high energy and power densities

Abstract

Although alkaline zinc-manganese dioxide batteries have dominated the primary battery applications, it is challenging to make them rechargeable. Here we report a high-performance rechargeable zinc-manganese dioxide system with an aqueous mild-acidic zinc triflate electrolyte. We demonstrate that the tunnel structured manganese dioxide polymorphs undergo a phase transition to layered zinc-buserite on first discharging, thus allowing subsequent intercalation of zinc cations in the latter structure. Based on this electrode mechanism, we formulate an aqueous zinc/manganese triflate electrolyte that enables the formation of a protective porous manganese oxide layer. The cathode exhibits a high reversible capacity of 225 mAh g−1 and long-term cyclability with 94% capacity retention over 2000 cycles. Remarkably, the pouch zinc-manganese dioxide battery delivers a total energy density of 75.2 Wh kg−1. As a result of the superior battery performance, the high safety of aqueous electrolyte, the facile cell assembly and the cost benefit of the source materials, this zinc-manganese dioxide system is believed to be promising for large-scale energy storage applications.

Nanostructured MnO2 as Electrode Materials for Energy Storage

“…Extensive works on MnO 2 materials for both batteries and supercapacitors in aqueous solutions can be found in Refs. [98,103,104,105,106,107,108,109,110]. …”

“…For example, γ -MnO 2 urchin-like nanostructures are grown using Mn 3 O 4 powder as raw material in H 2 SO 4 solution; α -MnO 2 urchin-like composed of single nanorods are obtained from KMnO 4 and H 2 SO 4 or from MnSO 4 ·H 2 O, K 2 S 2 O 8 and concentrated sulfuric acid. A redox reaction between MnSO 4 and (NH 4 ) 2 S 2 O 8 as an oxidizing agent can also be used [97,98,99,100,101,102,103,104,105,106,107,108,109,110,111,112,113,114,115,116,117]. Details of the synthesis of urchin-like α -MnO 2 are shown schematically in Figure 10.…”

3D zinc@carbon fiber composite framework anode for aqueous Zn–MnO2 batteries

“…[4][5][6][7][8] Among them, battery reactions based on reversible insertion of Na + , K + , Mg 2+ and Zn 2+ and hybrid ions in mild aqueous electrolyte have been considered as promising alternatives, because of their high safety, material abundance, non-ammability and environmentally friendly properties. 9,10 In an aqueous system, the narrow voltage window of water (1.23 V vs. SHE) restricts the options of electrode material, especially for the anode materials. Among these, rechargeable aqueous Zn/MnO 2 batteries are considered as one of the most attractive alternatives which have been extensively studied for several years.…”

Cryptomelane-Type KMn8O16 as Potential Cathode Material — for Aqueous Zinc Ion Battery

“…Among them, tunnel-type manganese oxides have been mostly investigated, including α-, β-, γ-, and δ-types MnO 2 (Xu et al, 2012, 2014; Alfaruqi et al, 2015a,b,c; Pan et al, 2016; Han et al, 2017; Zhang et al, 2017). Although considerable initial discharge capacity up to 200 mAh/g at low C -rate can be delivered, they suffer from the poor rate performance and a rapid capacity fading owing to the repeated phase transitions and the dissolution of Mn 2+ owing to Mn 3+ disproportionation upon cycling.…”