Unravelling the Mechanism of Rechargeable Aqueous Zn-MnO2 Batteries: Implementation of Charging Process by Electrodeposition of MnO2.,ChemSusChem

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Unravelling the Mechanism of Rechargeable Aqueous Zn-MnO2 Batteries: Implementation of Charging Process by Electrodeposition of MnO2.
ChemSusChem ( IF 7.5 ) Pub Date : 2020-06-04 , DOI: 10.1002/cssc.202001216
Jie Yang _{1,

2} , Jianyun Cao ₃ , Yudong Peng ₃ , Wenji Yang ₃ , Suelen Barg ₃ , Zhu Liu ₃ , Ian A Kinloch ₃ , Mark A Bissett ₃ , Robert A W Dryfe _{1,

2}

Affiliation

Poor cycling stability and mechanistic controversies have hindered the wider application of rechargeable aqueous Zn–MnO₂ batteries. Herein, direct evidence was provided of the importance of Mn²⁺ in this type of battery by using a bespoke cell. Without pre‐addition of Mn²⁺, the cell exhibited an abnormal discharge–charge profile, meaning it functioned as a primary battery. By adjusting the Mn²⁺ content in the electrolyte, the cell recovered its charging ability through electrodeposition of MnO₂. Additionally, a dynamic pH variation was observed during the discharge–charge process, with a precipitation of Zn₄(OH)₆(SO₄)⋅5H₂O buffering the pH of the electrolyte. Contrary to the conventional Zn²⁺ intercalation mechanism, MnO₂ was first converted into MnOOH, which reverted to MnO₂ through disproportionation, resulting in the dissolution of Mn²⁺. The charging process occurred by the electrodeposition of MnO₂, thus improving the reversibility through the availability of Mn²⁺ ions in the solution.

中文翻译：

揭示可充电水系 Zn-MnO2 电池的机理：通过电解沉积 MnO2 实现充电过程。

较差的循环稳定性和机理争议阻碍了可充电水系Zn-MnO ₂电池的更广泛应用。^{在此，通过使用定制电池提供了直接证据，证明了 Mn 2+}在此类电池中的重要性。如果没有预先添加 Mn ²⁺，电池就会表现出异常的放电-充电曲线，这意味着它充当原电池。通过调节电解液中Mn ^{2+含量，电池通过电沉积MnO}₂恢复充电能力。此外，在放电-充电过程中观察到动态pH值变化，Zn ₄ (OH) ₆ (SO ₄ )⋅5H ₂ O沉淀缓冲了电解质的pH值。与传统的Zn ²⁺嵌入机制相反，MnO ₂首先转化为MnOOH，MnOOH通过歧化作用恢复为MnO _{2 ，导致Mn}²⁺溶解。充电过程通过MnO ₂的电沉积发生，从而通过溶液中Mn ²⁺离子的可用性来提高可逆性。

更新日期：2020-06-04

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