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.
A key challenge faced by organic electrodes is how to promote the redox reactions of functional groups to achieve high specific capacity and rate performance. Here, we report a two-dimensional (2D) microporous covalent-organic framework (COF), poly(imide-benzoquinone), via in situ polymerization on graphene (PIBN-G) to function as a cathode material for lithium-ion batteries (LIBs). Such a structure favors charge transfer from graphene to PIBN and full access of both electrons and Li ions to the abundant redox-active carbonyl groups, which are essential for battery reactions. This enables large reversible specific capacities of 271.0 and 193.1 mAh g at 0.1 and 10 C, respectively, and retention of more than 86 % after 300 cycles. The discharging/charging process successively involves 8 Li and 2 Li in the carbonyl groups of the respective imide and quinone groups. The structural merits of PIBN-G will trigger more investigations into the designable and versatile COFs for electrochemistry.
Potassium-ion batteries (KIBs) are plagued by a lack of materials for reversible accommodation of the large-sized K ion. Herein we present, the Bi anode in combination with the dimethoxyethane-(DME) based electrolyte to deliver a remarkable capacity of ca. 400 mAh g and long cycle stability with three distinct two-phase reactions of Bi↔ KBi ↔K Bi ↔K Bi. These are ascribed to the gradually developed three-dimensional (3D) porous networks of Bi, which realizes fast kinetics and tolerance of its volume change during potassiation and depotassiation. The porosity is linked to the unprecedented movement of the surface Bi atoms interacting with DME molecules, as suggested by DFT calculations. A full KIB of Bi//DME-based electrolyte//Prussian blue of K Fe[Fe(CN) ] is demonstrated to present large energy density of 108.1 Wh kg with average discharge voltage of 2.8 V and capacity retention of 86.5 % after 350 cycles.
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