The Emerging of Aqueous Zinc-Based Dual Electrolytic Batteries.

As high performance and safety alternatives to the batteries with organic electrolytes, aqueous zinc-based batteries are still far from satisfactory in practical use because of the limitation of the intercalation reaction mechanism and the strict requirements for the cathodes. Very recently, zinc-based dual electrolytic batteries (DEBs), where the cathode and anode are both based on reversible electrolytic reactions, are emerging. It features with electrode-free configuration, thus avoiding the preliminary active materials or electrode fabrication procedures. Meanwhile, the new battery chemistry typically possesses a high specific capacity, output voltage, faster reaction rates, and long cycling life. Herein, the advances of the development of various zinc-based DEBs, including Zn-MnO2 , Zn-Br2 , and Zn-I2 DEBs, are systematically summarized. This review will focus on the working mechanisms of these batteries and how the decoupling catholyte and anolyte affect their output voltages. The perspectives of the opportunities and challenges are also suggested in the aspects of protecting zinc anode, enhancing volumetric energy density, suppressing fast self-discharge, and developing multifunctional integrated zinc-based DEBs.

An Electrolytic Zn-MnO2 Battery for High-Voltage and Scalable Energy Storage.

Zinc-based electrochemistry is attracting significant attention for practical energy storage owing to its uniqueness in terms of low cost and high safety. However, the grid-scale application is plagued by limited output voltage and inadequate energy density when compared with more conventional Li-ion batteries. Herein, we propose a latent high-voltage MnO2 electrolysis process in a conventional Zn-ion battery, and report a new electrolytic Zn-MnO2 system, via enabled proton and electron dynamics, that maximizes the electrolysis process. Compared with other Zn-based electrochemical devices, this new electrolytic Zn-MnO2 battery has a record-high output voltage of 1.95 V and an imposing gravimetric capacity of about 570 mAh g-1 , together with a record energy density of approximately 409 Wh kg-1 when both anode and cathode active materials are taken into consideration. The cost was conservatively estimated at

Complementary Operando Electrochemical Quartz Crystal Microbalance and UV/Vis Spectroscopic Studies: Acetate Effects on Zinc-Manganese Batteries.

Zinc-ion batteries, in which zinc ions and protons do intercalation and de-intercalation during battery cycling with various proposed mechanisms under debate, have been studied. Recently, electrolytic zinc-manganese batteries, exhibiting the pure dissolution-deposition behavior with a large charge capacity, have been accomplished through using electrolytes with Lewis acid. However, the complicated chemical environment and mixed products hinder the investigation though it is crucial to understand the detailed mechanism. Here, cyclic voltammetry coupled electrochemical quartz crystal microbalance (EQCM) and ultraviolet-visible spectrophotometry (UV-Vis) are respectively, for the very first time, used to study the transition from zinc-ion batteries to zinc electrolytic batteries by the continuous addition of acetate ions. These complementary techniques operando trace the mass and the composition evolution. The observed formation and dissolution of zinc hydroxide sulfate (ZHS) and manganese oxides evince the effect of acetate ions on zinc-manganese batteries from an alternative perspective. Both the amount of acetate and the pH value have large impacts on the capacity and Coulombic efficiency of the MnO2 electrode, and thus they should be optimized when constructing a full zinc-manganese battery with high rate capability and reversibility.