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中国物理学会期刊

应力对硅负极固体电解质界面膜生长和容量衰退的影响

CSTR:32037.14.aps.75.20251423

Effect of stress on the growth of solid electrolyte interphase films of silicon anodes and capacity fade

CSTR:32037.14.aps.75.20251423
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  • 锂离子电池由于具有高能量密度、无记忆效应、低自放电率以及长循环寿命等优点, 在储能领域得到了广泛应用. 然而, 电池老化问题, 特别是电池负极固体电解质界面(SEI)膜的形成及其持续生长, 是导致电池容量衰退的重要原因之一. 本研究聚焦于SEI膜生长过程中的力化双向耦合效应, 以硅负极为研究对象, 通过构建考虑电极颗粒体积膨胀与SEI膜动态生长的力化耦合模型, 探讨充放电过程中硅负极颗粒膨胀与SEI膜生成副反应动力学之间的相互作用机制. 研究表明, 应力增大了副反应电流密度, 加速SEI膜生长, 从而加剧电池容量衰退. 此外, 计算结果显示在颗粒不开裂的前提下, 增大硅颗粒半径与降低电池放电深度可有效提高电池容量保持率. 本研究为高性能锂离子电池的设计提供了理论指导.

    Lithium-ion batteries (LIBs) are widely used in energy storage owing to their high energy density and long cycle life, but battery aging, especially capacity fade associated with the formation and growth of the solid electrolyte interphase (SEI) film on the anode, limits service life and cycling performance. Although many efforts have been made to the modeling of SEI chemistry and transport, the mechano-chemical coupling between stress evolution and SEI film growth-induced capacity loss in silicon-based anodes remains unclear. Building on the classical Doyle-Fuller-Newman cell model, we describe diffusion-limited SEI film growth and introduce a local hydrostatic stress term into the overpotential of the SEI-forming side reaction, thereby obtaining a stress-coupled kinetic equation for the side-reaction current density. This framework captures how lithiation-induced particle expansion generates hydrostatic stress, how this stress modifies electrolyte-reduction kinetics, and how the resulting SEI film thickening feeds back to influence further stress evolution. Simulations show that hydrostatic stress exponentially amplifies the side-reaction current density, accelerates SEI film accumulation, and thereby intensifies capacity fade, while neglecting stress coupling underestimates the SEI film growth rate and degradation severity. Parametric studies reveal that, within a non-cracking regime, increasing the silicon particle radius reduces the normalized SEI film thickness and improves capacity retention, whereas decreasing the depth of discharge shortens the time window for side reactions, suppresses SEI film growth, and mitigates degradation. By establishing this mechano-chemical framework, the study clarifies the link between SEI film growth and capacity loss and provides theoretical support for lifetime prediction and failure mitigation in next-generation high-energy-density LIBs.

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