论文标题

由于Na/na $^+$ redox反应而导致的GE电极中体积变化和相关应力的测量

Measurement of Volume Changes and Associated Stresses in Ge Electrodes Due to Na/Na$^+$ Redox Reactions

论文作者

Rakshit, Subhajit, Pakhare, Akshay S., Ruiz, Olivia, Khoshi, M. Reza, Detsi, Eric, He, Huixin, Sethuraman, Vijay A., Nadimpalli, Siva P. V.

论文摘要

将原位电化学细胞与无定形锗(A-GE)组装为工作电极和钠箔作为参考和反电极。在电静态循环期间,实时测量了由于电化学反应与钠的电化学反应引起的A-GE电极产生的应力。针对钠循环循环专门设计的图案A-GE电极,并使用AFM测量相应的体积变化。据观察,A-GE的屈态/脱位会导致体积变化超过300%,这与文献一致。潜在和应力反应表明,在第一个屈态过程中,A-GE膜发生不可逆的变化,但是随后的解次/屈服周期是可逆的。胶片的应力反应在初次屈曲后达到了稳态,并且在质量上与GE在静态过程中的响应(即初始线性弹性响应,然后是对膜的广泛塑性变形,以适应大量体积变化)。然而,尽管离子更大,但与锂化相比,GE的屈态导致了较低的应力水平。因此,在屈态过程中,与塑性变形相关的机械耗散损失比静态较低。

In situ electrochemical cells were assembled with an amorphous germanium (a-Ge) film as working electrode and sodium foil as reference and counter electrode. The stresses generated in a-Ge electrodes due to electrochemical reaction with sodium were measured in real-time during the galvanostatic cycling. A specially designed patterned a-Ge electrode was cycled against sodium and the corresponding volume changes were measured using an AFM; it was observed that sodiation/desodiation of a-Ge results in more than 300% volume change, consistent with literature. The potential and stress response showed that the a-Ge film undergoes irreversible changes during the first sodiation process, but the subsequent desodiation/sodiation cycles are reversible. The stress response of the film reached steady-state after the initial sodiation and is qualitatively similar to the response of Ge during lithiation, i.e., initial linear elastic response followed by extensive plastic deformation of the film to accommodate large volume changes. However, despite being bigger ion, sodiation of Ge generated lower stress levels compared to lithiation. Consequently, the mechanical dissipation losses associated with plastic deformation are lower during sodiation process than it is for lithiation.

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