Building a High-Potential Silver-Sulfur Redox Reaction Based on the Hard-Soft Acid-Base Theory.

Sulfur holds immense promise for battery applications owing to its abundant availability, low cost, and high capacity. Currently, sulfur is commonly combined with alkali or alkaline earth metals in metal-sulfur batteries. However, these batteries universally face challenges in cycling stability due to the inevitable issue of polysulfide dissolution and shuttling. Additionally, the inferior stability of metal sulfide discharge compounds results in low S0/S2- redox potentials (<-0.41 V vs SHE). Herein, we leverage the principle of the hard-soft acid-base theory to introduce a novel silver-sulfur (Ag-S) battery system, which operates on the reaction between the soft acid of Ag+ and the soft base of S2-. Due to their high reaction affinity, the discharge compound of silver sulfide (Ag2S) is intrinsically insoluble and fundamentally stable. This not only resolves the polysulfide dissolution issue but also leads to a predominantly high S0/S2- redox potential (+1.0 V vs. SHE). We thus exploit the Ag-S reaction for a primary zinc battery application, which exhibits a high capacity of ∼620 mAh g-1 and a high voltage of ∼1.45 V. This work offers valuable insights into the application of classic chemistry theories in the development of innovative energy storage devices.

Building a Rechargeable Voltaic Battery via Reversible Oxide Anion Insertion in Copper Electrodes.

Voltaic pile, the very first battery built by humanity in 1800, plays a seminal role in battery development history. However, the premature design leads to the inevitable copper ion dissolution issue, which dictates its primary battery nature. To address this issue, solid-state electrolytes, ion exchange membranes, and/or sophisticated electrolytes are widely utilized, leading to high costs and complicated cell configuration. Herein, we build a rechargeable zinc-copper voltaic battery from simple and cheap electrolyte/separator materials, thus eliminating the need to use the above components. Notably, our battery leverages the Zn4SO4(OH)6·xH2O precipitation in ZnSO4 electrolytes, a common side reaction in zinc batteries, to provide a "locally alkaline" environment for copper electrodes. Consequently, oxide (O2-) anion insertion takes place and readily transforms copper to copper(I) oxide (Cu2O) without any copper ion dissolution issue. Therefore, this battery realizes a high capacity of ∼370 mA h g-1 and a long cycling of ∼500 cycles. Our work provides an innovative approach to stabilize anion insertion in metal electrodes for energy storage.

Trivalent Indium Metal as a High-Capacity, High-Efficiency, Low-Polarization, and Long-Cycling Anode for Aqueous Batteries.

Aqueous batteries using multivalent metals hold great promise for energy storage due to their low cost, high energy, and high safety. Presently, divalent metals (zinc, iron, nickel, and manganese) prevail as the leading choice, which, however, suffer from low Coulombic efficiency or dendrite growth. In stark contrast, trivalent metals have received rare attention despite their capability to unlock unique redox reactions. Herein, we investigate trivalent indium as an innovative and high-performance metal anode for aqueous batteries. The three-electron In3+/In redox endows a high capacity of ∼700 mAh g-1, on par with the Zn metal. Besides, indium exhibits a suitable redox potential (-0.34 V vs standard hydrogen electrode) and dendrite-free plating process, which renders an ultrahigh Coulombic efficiency of 99.3-99.8%. More surprisingly, it features an exceedingly low polarization of 1 mV in symmetrical cells, which is 1-2 orders of magnitude lower than any reported metals. The In-MnO2 full cell also delivers impressive performance, with a cell voltage of ∼1.2 V, a high capacity of ∼330 mAh g-1, and a long cycling time of 680 cycles. Our work exemplifies the efficacy of exploiting trivalent metals as an excellent metal anode, which provides an exciting direction for building high-performance aqueous batteries.