Critical Contribution of Imbalanced Charge Loss to Performance Deterioration of Si-Based Lithium-Ion Cells during Calendar Aging

Abstract

Increasing the energy density of lithium-ion batteries, and thereby reducing costs, is a major target for industry and academic research. One of the best opportunities is to replace the traditional graphite anode with a high-capacity anode material, such as silicon. However, Si-based lithium-ion batteries have been widely reported to suffer from a limited calendar life for automobile applications. Heretofore, there lacks a fundamental understanding of calendar aging for rationally developing mitigation strategies. Both open-circuit voltage and voltage-hold aging protocols were utilized to characterize the aging behavior of Si-based cells. Particularly, a high-precision leakage current measurement was applied to quantitatively measure the rate of parasitic reactions at the electrode/electrolyte interface. The rate of parasitic reactions at the Si anode was found 5 times and 15 times faster than those of LiNi0.8Mn0.1Co0.1O2 and LiFePO4 cathodes, respectively. The imbalanced charge loss from parasitic reactions plays a critical role in exacerbating performance deterioration. In addition, a linear relationship between capacity loss and charge consumption from parasitic reactions provides fundamental support to assess calendar life through voltage-hold tests. These new findings imply that longer calendar life can be achieved by suppressing parasitic reactions at the Si anode to balance charge consumption during calendar aging.

Chemical contributions to silicon anode calendar aging are dominant over mechanical contributions

“…Calendar life limitations have been more challenging to understand and overcome (Zilberman et al, 2019a;Zilberman et al, 2019b;Cai et al, 2023). Si anode calendar life is inferior to graphite and remains below targets set for EVs (McBrayer et al, 2021b;Schulze et al, 2022;Kalaga et al, 2018;Zilberman et al, 2019b).…”