Insights into the Sodiation Kinetics of Si and Ge Anodes for Sodium-Ion Batteries
Peer reviewed, Journal article
Published version
Permanent lenke
https://hdl.handle.net/11250/3098184Utgivelsesdato
2023Metadata
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Originalversjon
10.1149/1945-7111/ad0075Sammendrag
Group IVA elements exhibit interesting Na storage capabilities due to the success of their Li alloy analogues. However, beyond hard carbon, they remain poorly understood as anodes for sodium-ion batteries (SIBs). Here, kinetic investigations of the electrochemical sodiation of Si and Ge are conducted using liquid electrolytes and half-cell configurations. Sodiation of Ge is found to be kinetically limited rather than thermodynamically limited. Either increasing temperature or decreasing sodiation rate can facilitate easier transformations from Ge to Na-Ge phases. A critical temperature seems to exist between 50 °C and 60 °C, beyond which a higher sodiation capacity is evident. The phase transformations are analyzed using Kolmogorov–Johnson–Mehl–Avrami theory. Following a one-dimensional growth, the Ge to NaGe4 is determined to be diffusion limited whereas NaGe4 to Na1+xGe is controlled by reaction speed. Moreover, the Arrhenius equation is employed to investigate the temperature dependence on both phase transformations, giving activation energies of ∼50 kJ·mol−1 and ∼70 kJ·mol−1, respectively. Schematic models are proposed to elucidate the sodiation mechanisms, potentially influencing sought-after advancements in cell formats and classifications. Not only does this work lay the foundation for efforts on the Ge-based anodes, but also provides analogous kinetic information to Si/Sn-based ones for SIBs.