Rechargeable aqueous zinc-manganese oxide (Zn/MnO₂) batteries using Mn²⁺ as the electrolyte additive have recently attracted remarkable attention owing to their largely improved cycling stability. Herein, we find that the Zn/MnO₂ batteries with Mn²⁺ additive still exhibit rapid capacity fading when cycling between 0.8 and 1.6 V vs. Zn/Zn²⁺, its improved performance is only observed when charged to a higher slope region (>1.6 V), which suggests that the improved performance of Mn²⁺ added Zn/MnO₂ is not caused by suppressing the dissolution of MnO₂ cathode. Inspired by this discovery, successive electrochemcial conversion reactions are scrutinized and proved for evaluating the performance of the Zn/MnO₂ batteries after using Mn²⁺ as the electrolyte additive. By adding a certain amount of Mn²⁺ into the electrolyte, the battery can improve the capacity and cycling abilitily through converted electrodepostion of Mn²⁺. Specifically, the zinc sulfate hydroxide hydrate (Zn₄SO₄·(OH)₆·4H₂O) large-flake can initiate the generation of zinc vernadite nanosheets (Zn_xMnO(OH)_y) during the charge process (around 1.5 V vs. Zn/Zn²⁺), and then the zinc vernadite nanosheets can reversibly re-back to Zn₄SO₄·(OH)₆·4H₂O during the discharge process. Importantly, part of zinc vernadite nanosheets irreversibly transform into tunnel-like MnO₂ nanocrystalline material when charging higher than 1.6 V vs. Zn/Zn²⁺, which can improve the specific capacity of Zn/MnO₂ batteries in subsequent cycles and then make the Zn/MnO₂ batteries exhibit excellent cycles stability. Finally, through a special zinc/carbon nanotube (Zn/CNT) battery, this successive electrochemcial conversion reactions are further verified.

使用Mn ²⁺作为电解质添加剂的可再充电的含水锌锰氧化物（Zn / MnO ₂）电池由于其循环稳定性的大幅提高，近来引起了人们的极大关注。在这里，我们发现具有Mn ²⁺添加剂的Zn / MnO ₂电池在0.8至1.6 V的电压与Zn / Zn ²⁺之间循环时仍显示出快速的容量衰减，其性能只有在充电到较高的斜率区域时才能观察到（ > 1.6 V），这表明添加Mn ^2+的Zn / MnO _2的性能改善不是由于抑制MnO ₂的溶解而引起的阴极。受这一发现的启发，对连续的电化学转化反应进行了仔细的考察，并证明了在使用Mn ²⁺作为电解质添加剂后可用于评估Zn / MnO ₂电池的性能。通过将一定量的Mn ^2+添加到电解液中，电池可以通过转换后的Mn ²⁺电极沉积来提高容量和稳定循环。具体地说，在充电过程中（约1.5 V），氢氧化锌水合物（Zn ₄ SO ₄ ·（OH）₆ ·4H ₂ O）大片状可以引发锌白云母纳米片（Zn _x MnO（OH）_y）的生成。与锌/锌²⁺），然后将锌水羟锰矿纳米片能够可逆地重新返回到锌₄ SO ₄ ·（OH）₆ ·4H ₂ ö在放电过程。重要的是，当锌与锌/ Zn ^2+的充电电压高于1.6 V时，部分锌白云母纳米片不可逆地转变为隧道状MnO ₂纳米晶体材料，这可以提高Zn / MnO ₂电池在随后的循环中的比容量，然后使Zn / MnO ₂电池具有出色的循环稳定性。最后，通过特殊的锌/碳纳米管（Zn / CNT）电池，进一步验证了这种连续的电化学转化反应。