The detrimental ratio (ρ): A critical metric complementing coulombic loss for long calendar-life silicon-based lithium-ion batteries

Silicon (Si) is a promising high-capacity anode in lithium-ion batteries but suffers from chronic chemical degradation and capacity fading during calendar aging, greatly hindering its automobile applications. Electrolyte engineering currently relies on conventional evaluation criteria of reducing coulombic consumption, which implicitly presume its equivalence to irreversible capacity loss and complicates battery development. We introduce the detrimental ratio ρ to quantify the fraction of parasitic species that permanently degrades active material. This metric is independent and crucially complements total coulombic consumption for accurate performance evaluation. We systematically investigate multiple electrolyte formulations using high-precision leakage current measurements, open-circuit-voltage experiments, and post-mortem characterizations. Although some electrolytes exhibit similarly low coulombic consumption, they diverge significantly in capacity retention and ρ. Especially, dimethyl-carbonate-based localized-high concentration electrolyte can synergically achieve low coulombic consumption and detrimental ratio ρ during calendar aging, owing to its chemically inert and structurally resilient solid-electrolyte interface with minimal isolated Si material. By contrast, increasing fluoroethylene carbonate (FEC) additive content suppresses electrolyte breakdown but suffers aggravated chemical degradation of more LixSi isolation for irreversible capacity loss with a rising ρ. This study critically reveals that the chemistry-characteristic detrimental ratio ρ establishes physically informed performance evaluation to pave the way for accelerating battery development.