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<p>Lithium-ion batteries can fail catastrophically through thermal runaway, but the key trigger has remained unclear. Here we show that the most harmful cause is lithium oxidation reaction (LOR). This makes two types of high-energy-density battery surprisingly most dangerous: all-solid-state batteries with cracked solid separators, whether from manufacturing defects, high-pressure assembly or electrochemical cycling, and batteries with non-flammable liquid electrolytes. In both batteries, oxygen evolved from an oxide cathode passes directly to an anode, triggering highly energetic LOR. In contrast, traditional carbonate- and ether-based electrolytes are safer because they can consume O<sub>2</sub> in transit, alleviating or avoiding LOR. These findings apply to both lithium metal and lithiated anodes such as graphite. Safe electrolytes are thus either solid ion conductors that stop O<sub>2</sub> crossover under all conditions or materials that scavenge O<sub>2</sub> through low-exothermic reactions.</p>

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Metrics for evaluating safe electrolytes in energy-dense lithium batteries

  • 期刊论文

  • 发表日期：

    2025年10月30日

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  • Chao-Yang Wang,
  • Kaiqiang Qin,
  • Shanhai Ge,
  • Nitesh Gupta,
  • Tatsuro Sasaki,
  • Koichiro Aotani

摘要

Lithium-ion batteries can fail catastrophically through thermal runaway, but the key trigger has remained unclear. Here we show that the most harmful cause is lithium oxidation reaction (LOR). This makes two types of high-energy-density battery surprisingly most dangerous: all-solid-state batteries with cracked solid separators, whether from manufacturing defects, high-pressure assembly or electrochemical cycling, and batteries with non-flammable liquid electrolytes. In both batteries, oxygen evolved from an oxide cathode passes directly to an anode, triggering highly energetic LOR. In contrast, traditional carbonate- and ether-based electrolytes are safer because they can consume O2 in transit, alleviating or avoiding LOR. These findings apply to both lithium metal and lithiated anodes such as graphite. Safe electrolytes are thus either solid ion conductors that stop O2 crossover under all conditions or materials that scavenge O2 through low-exothermic reactions.