Quantitative insights for diagnosing performance bottlenecks in lithium–sulfur batteries

Abstract

Lithium–sulfur (Li–S) batteries hold significant promise for electric vehicles and aviation due to their high energy density and cost-effectiveness. However, understanding the root causes of performance degradation remains a formidable challenge, as the interplay of multiple factors obscures key failure mechanisms. A major limitation has been the inability to quantify soluble sulfur species within practical detection limits accurately and to correlate electrochemical processes with associated physical inventory changes. Here, we introduce the high-performance liquid chromatography-ultraviolet spectroscopy and gas chromatography sequential characterization (HUGS) toolkit, capable of precisely quantifying seven distinct sulfur and polysulfide species at concentrations as low as 40 ppb. HUGS has been successfully applied to practical coin and pouch cells without requiring cell modification. Furthermore, our self-developed software, Dr HUGS, enhanced the data analysis speed by over 30 times, enabling multi-source data integration and delivering comprehensive analysis results within minutes. Using HUGS, we identify significant capacity losses from inactive lithium and sulfur during initial cycles and sulfide-rich solid–electrolyte interphase (SEI) formation on the anode during later cycles. Notably, our findings reveal that soluble polysulfides have minimal contributions to capacity loss, challenging long-standing assumptions. Moreover, HUGS demonstrates that constant-pressure setups in Li–S pouch cells improve compositional uniformity compared to constant-gap configurations. For sulfurized polyacrylonitrile (SPAN) cathodes, unique issues such as non-sulfide SEI formation and lithium pulverization are observed, which can be mitigated through localized high-concentration electrolytes to enhance lithium inventory retention. By enabling precise quantification of critical inventory components, HUGS provides transformative insights into failure mechanisms across various electrolytes and cathode chemistries, guiding rational design strategies for next-generation energy storage systems.