Lithium-ion batteries (LiBs) have been successfully utilized as power sources in various applications ubiquitous in our daily lives, ranging from portable electronic devices to electric vehicles. To meet the increasing energy demand, however, development of LiBs with a higher energy density is inevitable. Using silicon (Si) as an anode is promising due to its high theoretical capacity (approximately 4200 mAhg^-1), appropriate operating voltage (~0.4 V vs. Li/Li⁺), abundance, and environmentally benign nature.¹ Despite the aforementioned advantages, several challenges remain before the commercial utilization of Si anodes, namely the low conductivity of its readily-formed surface oxide (SiO₂), a large volume change (up to 400 %) during lithiation/delithiation, and the instability of Si/electrolyte interface (SiEI).^2-3 As the large volume change leads to fracture and continuous evolution of SiEI, achieving a stable SiEI is a key to developing successful LiBs with Si anodes.

Water, which is known to react with LiPF₆ salt in carbonate-based electrolytes to generate corrosive hydrofluoric acid (HF),⁴ is a source for the electrode/electrolyte interface destabilization. Thus, it is essential to understand how the presence of even trace amounts of water in the system affects the interfacial chemistry of the LiB electrodes. While the performance of LiBs with graphite or lithium titanate negative electrodes have been previously studied with excess water in the electrolyte,^5-6 information on the effect of water concentration in the electrolyte on Si anodes, and the SiEI in particular, is limited.

In this work, we evaluated the electrochemical performance of Si anodes in a standard electrolyte (1.2 M LiPF₆ in EC:EMC (3:7 wt%)) with varying concentration of water (10 - 1,000 ppm). Subsequent analyses on the cycled Si anodes were performed utilizing a variety of surface and bulk characterization techniques. The surface chemistry (e.g., composition and evolution) of SiEI was analyzed using Fourier-transform infrared spectroscopy (FTIR), Raman spectroscopy, time-of-flight secondary ion mass spectrometry (TOF-SIMS), and X-ray photoelectron spectroscopy (XPS). Surface morphologies of cycled Si anodes were measured with tapping-mode atomic force microscopy (AFM), and the surface resistivities were mapped in contact-mode with scanning spreading resistance microscopy (SSRM). The information obtained is utilized to understand water concentration effects on the properties, reactivity, and evolution of the SiEI and the electrochemical cell performance.

References

1. Feng, K.; Li, M.; Liu, W.; Kashkooli, A. G.; Xiao, X.; Cai, M.; Chen, Z., Silicon-Based Anodes for Lithium-Ion Batteries: From Fundamentals to Practical Applications. Small 2018, 14 (8), 1702737.
2. Chae, S.; Ko, M.; Kim, K.; Ahn, K.; Cho, J., Confronting Issues of the Practical Implementation of Si Anode in High-Energy Lithium-Ion Batteries. Joule 2017, 1 (1), 47-60.
3. Philippe, B.; Dedryvere, R.; Allouche, J.; Lindgren, F.; Gorgoi, M.; Rensmo, H.; Gonbeau, D.; Edstrom, K., Nanosilicon Electrodes for Lithium-Ion Batteries: Interfacial Mechanisms Studied by Hard and Soft X-ray Photoelectron Spectroscopy. Chem. Mater. 2012, 24 (6), 1107-1115.
4. Xu, K., Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries. Chem. Rev. 2004, 104 (10), 4303-4417.
5. Burns, J. C.; Sinha, N. N.; Jain, G.; Ye, H.; VanElzen, C. M.; Scott, E.; Xiao, A.; Lamanna, W. M.; Dahn, J. R., The impact of intentionally added water to the electrolyte of Li-ion cells. I. Cells with graphite negative electrodes. J. Electrochem. Soc. 2013, 160 (11), A2281-A2287.
6. Burns, J. C.; Sinha, N. N.; Jain, G.; Ye, H.; Van Elzen, C. M.; Scott, E.; Xiao, A.; Lamanna, W. M.; Dahn, J. R., The impact of intentionally added water to the electrolyte of Li-ion cells: II. Cells with lithium titanate negative electrodes. J. Electrochem. Soc. 2014, 161 (3), A247-A255.