锌枝晶成核及生长溶解过程的超分辨成像研究

在目前的电化学储能技术中，金属空气电池是一类具有广泛应用前景的电池。其中，由于高安全性，高重量比容量，高储量和低成本的优点，锌空气电池（ZABs）具有巨大的发展潜力。然而，锌枝晶的形成会导致电池容量损失和循环寿命的减少，严重制约了锌空气电池的发展。本文针对锌空气电池中的枝晶问题，利用全内反射暗场显微镜在纳米尺度上观测研究了枝晶生长和溶解过程的细节。在单核水平上证明了电流密度和电解液浓度对锌枝晶的成核、生长时间和生长方向具有重要影响。在低盐浓度和高电流密度的条件下，枝晶会快速成核，更容易沉积为树枝状枝晶。揭示了沉积形态（苔藓状或树枝状）高度受制于局部反应动力学，进一步证实了锌离子的耗尽以及副反应的发生是树枝状枝晶形成的关键因素。通过研究锌枝晶的溶解过程，证明了充电电流密度对宏观孤晶的生成起主导作用，放电电流密度对纳米孤晶的产生时间和生成数量有重要影响。随着充电电流密度的增大，宏观孤晶数量减少。随着放电电流密度的增大，纳米孤晶产生阶段和数量均增加。揭示了孤晶的总数量和固体电解质界面膜（SEI）的转化共同影响电池的库伦效率。除此之外，还对比了ZnSO₄、PEI添加剂和Zn(OTf)₂电解液中孤晶及SEI的产生阶段和数量的不同，证明设计合适的电解液可以有效提高开发长寿命锌空气电池的使用寿命。

Metal-air batteries are considered to be a promising class of batteries among the electrochemical energy storage technologies. In particular, zinc-air batteries (ZABs) have powerful potential in virtue of their high safety, high specific capacity by weight, high reserves and low cost. However, dendrites lead to capacity loss and reduction in cycle life, which limit the development of Zn-air batteries. Herein, aiming at the dendrite problem in zinc-air batteries, we employed total internal reflection dark field microscopy to observe the details of the nanoscopic dendrite growth and dissolution process. The effects of current density and electrolyte concentration on zinc nucleation, growth time and growth direction were demonstrated at the single-nuclei level. With a low electrolyte concentration and high current density，zinc nucleates quickly and is easier to deposit as dendrites. The deposition morphology, mossy or dendritic, was revealed to be highly constrained by local reaction kinetics, confirming that depletion of zinc ions as well as side reactions are key factors in the formation of dendritic dendrites. The charge current density plays a dominant role in the generation of macroscopic orphaning, and the discharge current density has an important effect on the generation stage and amount of nanoscopic orphaning during the dissolution process of zinc dendrites. With the increase of charge current density, the quantity of macroscopic orphaning decreases. The discharge current density increases, and the quantity of generation stage and nanoscopic orphaning increases. It is revealed that both the quantity of orphaning and the conversion of solid electrolyte interface affect the coulombic efficiency of the cell. In addition, the generation stage, the quantity of orphaning and solid electrolyte interface in ZnSO₄, PEI additives and Zn(OTf)₂ electrolytes were compared, demonstrating that the design of a suitable electrolyte is necessary to develop long-life Zn air batteries.

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