In Situ Probing of Mass Exchange at the Solid Electrolyte Interphase in Aqueous and Nonaqueous Zn Electrolytes with EQCM-D
In Situ Probing of Mass Exchange at the Solid Electrolyte Interphase in Aqueous and Nonaqueous Zn Electrolytes with EQCM-D
复制标题
使用 EQCM-D 原位探测水性和非水性锌电解质中固体电解质界面的质量交换
DOI：
10.1021/acsami.1c00565
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发表时间：
2021
影响因子：
9.5
通讯作者：
Sa, Niya
中科院分区：
文献类型：
--
作者：
Cora, Saida;Ahmad, Suzalmurni;Sa, Niya
多价化学为锂离子储能技术之外的发展提供了令人着迷的好处，并引起了广泛的研究兴趣。在多价候选材料中，金属锌阳极以较低的成本提供了有吸引力的高体积容量，用于设计二次离子电池。然而，锌电解质/阳极边界处的界面质量交换很复杂。人们最不了解的固体电解质界面（SEI）与可逆金属沉积同时发生，其动态进展尚不清楚且难以捕获。研究这种动态界面的一个主要挑战是缺乏原位分析方法，无法提供直接的传质信息来重现空气敏感、高 iRdrop 的非水电解质环境中的实际电池工作条件。这里报告的工作揭示了利用多谐波石英晶体微天平和耗散方法与光谱分析相结合，对锌电解质/电极界面处的复杂动态SEI进行了深入分析。观察到非水 Zn(TFSI)2 电解质中 SEI 形成与水性 ZnCl2 电解质中可逆锌沉积的关键差异。在非水锌电解质的初始电化学循环中，显着地观察到相对于重量质量变化的大量不成比例的库仑损失，结果表明原位形成了离子可渗透的 SEI 层，其成分具有丰富的有机 S 和 N 成分。进一步的泛音相关耗散分析表明，在非水 Zn(TFSI)2 电解质的早期 SEI 形成过程中，电极界面处的粘弹性发生了变化。
Multivalent chemistry provides intriguing benefits of developing beyond lithium ion energy storage technologies and has drawn extensive research interests. Among the multivalent candidates, metallic zinc anodes offer an attractive high volumetric capacity at a low cost for designing the secondary ion batteries. However, the interfacial mass exchange at the Zn electrolyte/anode boundary is complicated. The least understood solid electrolyte interphase (SEI) occurs simultaneously with the reversible metal deposition, and its dynamic progression is unclear and difficult to capture. One major challenge to investigate such a dynamic interface is the lack ofin situanalytical methods that offer direct mass transport information to reproduce the realistic battery operating conditions in an air-sensitive, nonaqueous electrolyte environment with a highiRdrop. Work reported here reveals an in-depth analysis of the complex and dynamic SEI at the Zn electrolyte/electrode interface utilizing a multiharmonic quartz crystal microbalance with a dissipation method combined with the spectroscopic analysis. Key differences are observed for the SEI formation in the nonaqueous Zn(TFSI)2electrolyte in contrast to the aqueous ZnCl2electrolyte for reversible Zn deposition. A large disproportional loss of coulombs relative to the gravimetric mass change is prominently observed at the initial electrochemical cycles in the nonaqueous Zn electrolyte, and results suggest anin situformation of an ionically permeable SEI layer that is compositionally featured with a rich content of organic S and N components. Further overtone-dependent dissipation analysis implies the changes in viscoelasticity at the electrode interface during the early SEI formation in the nonaqueous Zn(TFSI)2electrolyte.