A novel electrolyte additive, prop-1-ene-1,3-sultone (PES), has recently attracted great attention due to its formation of effective solid–electrolyte interphase (SEI) films and remarkable cell performance in lithium-ion batteries. Herein, the reductive decomposition of PES is investigated through density functional calculations combined with a self-consistent reaction field method, in which the bulk solvent effect is accounted for by the geometry optimization and transition-state search. We examine three ring-opening pathways, namely, O–C, S–C, and S–O bond-breaking processes. Our calculations reveal that the Li⁺ ion plays a pivotal role in the reductive decomposition of PES. While the most kinetically favored process—the S–O bond breaking—is effectively blocked via the formation of an intermediate structure, namely, the Li⁺-participated seven-membered ring, the other decomposition processes via O–C and S–C bond breaking lead to stable decomposition products. The constituents of SEI observed in previous experimental studies, such as RSO₃Li and ROSO₂Li, can be reasonably understood as the decomposition products resulting from O–C and S–C bond breaking, respectively.

中文翻译：

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锂离子电池阳极上电解质-固相间形成过程中丙-1-烯-1,3-内酯的还原分解机理

新型电解质添加剂丙-1-烯-1,3-磺内酯（PES）由于其形成有效的固体-电解质中间相（SEI）膜和锂离子电池卓越的电池性能而受到了广泛的关注。本文中，通过密度泛函计算与自洽反应场方法相结合，研究了PES的还原分解，在该方法中，通过几何优化和过渡态搜索解决了整体溶剂效应。我们研究了三种开环途径，即OC，SC和S-O键断裂过程。我们的计算表明，Li ⁺离子在PES的还原分解中起关键作用。虽然最动力学上受支持的过程（S–O键断裂）通过形成中间结构（即Li ⁺参与的七元环）有效地被阻止，但其他分解过程通过O–C和S–C键破坏导致稳定的分解产物。在先前的实验研究中观察到的SEI成分，例如RSO ₃ Li和ROSO ₂ Li，可以合理地理解为分别由O-C和S-C键断裂产生的分解产物。