Degradation and expansion of lithium-ion batteries with silicon/graphite anodes: Impact of pretension, temperature, C-rate and state-of-charge window

Abstract

Lithium-ion batteries with silicon/graphite (Si/Gr) anodes achieve higher energy densities but face challenges such as rapid capacity fade, resistance growth, and complex expansion behavior under various cycling conditions. This study systematically addresses these challenges through a comprehensive test matrix to investigate the effects of pressure, temperature, state-of-charge (SoC) windows, and charge rates (C-rates) on the evolution of expansion, resistance, and capacity behavior over the lifetime of the battery. Increasing the applied pressure between 34 and 172 kPa reduced both reversible and irreversible expansion per cycle, as well as resistance growth over time, without significantly impacting capacity fade. Electrochemical Impedance Spectroscopy (EIS) confirmed that increased pressure lowered initial solution resistance and mitigated the further growth of the solution and solid electrolyte interphase (SEI) resistance. Elevated temperature (45°C) extended battery cycle life despite an initial increase in resistance. The lifetime impedance increase under 45°C was dominated by SEI resistance. Consistent with prior studies, operating in a narrow SoC window at high SoC minimized capacity loss. Additionally, charge rates up to 2C had a limited effect on the overall degradation trends. Incremental capacity analysis (ICA) and differential voltage analysis (DVA) identified lithium inventory loss (LLI) as the primary cause of pre-knee degradation, whereas post-knee degradation resulted from a combination of LLI and anode-active material loss, particularly silicon. The deeper understanding of degradation mechanisms in batteries with Si/Gr anodes provided by this work enables the optimal packaging design and selection of operating conditions for the battery management system to extend battery cycle life. • High pressure (34–172 kPa) reduced resistance/expansion with limited capacity impact. • Cycling at 45°C extended battery life but caused more early-life resistance growth. • Irreversible expansion closely aligned with resistance patterns at 25°C and 0°C. • ICA/DVA identified LLI pre-knee and a combined LLI, LAM-Anode (Si) effect post-knee. • EIS revealed SEI resistance as the dominant contributor to kinetic degradation.

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