Reversible Transformation of a Zinc Salt-Boosted High Areal Capacity Manganese Dioxide Cathode for Energy-Dense and Stable Aqueous Zinc Batteries

A brightener-inspired polymer interphase enables highly reversible aqueous Zn anodes via suppressing side-reactions and manipulating the nucleation process. Aqueous Zn anodes have been revisited for their intrinsic safety, low cost, and high volumetric capacity; however, deep-seated issues of dendrite growth and intricate side-reactions hindered their rejuvenation. Herein, a “brightener-inspired” polyamide coating layer which elevates the nucleation barrier and restricts Zn 2+ 2D diffusion is constructed to effectively regulate the aqueous Zn deposition behavior. Importantly, serving as a buffer layer that isolates active Zn from bulk electrolytes, this interphase also suppresses free water/O 2 -induced corrosion and passivation. With this synergy effect, the polymer-modified Zn anode produces reversible, dendrite-free plating/stripping with a 60-fold enhancement in running lifetime (over 8000 hours) compared to the bare Zn, and even at an ultrahigh areal capacity of 10 mA h cm −2 (10 mA cm −2 for 1 h, 85% depth of discharge). This efficient rechargeability for Zn anodes enables a substantially stable full-cell paired with a MnO 2 cathode. The strategy presented here is straightforward and scalable, representing a stark, but promising approach to solve the anode issues in advanced Zn batteries.

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.