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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研究

Study on the Effects of Stress on the Growth of Solid Electrolyte Interphase Films of Silicon Anodes and Capacity Fade

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  • 锂离子电池由于其高能量密度、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膜(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) have been widely used in the field of energy storage due to their advantages such as high energy density, no memory effect, low self-discharge rate, and long cycle life. However, battery aging remains one of the main bottlenecks restricting further development. In particular, the formation and continuous growth of the solid electrolyte interphase (SEI) film on the anode is a key factor leading to capacity fade. This study focuses on the bidirectional mechano-chemical coupling effects during SEI growth. Using a silicon anode as the model system, we develop a coupling framework that accounts for active-particle volumetric expansion and stress-dependent interfacial side-reaction kinetics together with dynamic SEI thickening, to elucidate their interactions during charge/discharge. Simulations show that hydrostatic stress increases the side-reaction current density, accelerates SEI growth, and thereby exacerbates capacity degradation. Parametric analysis further indicates that, within a non-cracking particle-size window, increasing the silicon particle radius improves capacity retention, while lowering the depth of discharge (i.e., using a lower cutoff voltage) shortens the reactive time window, suppresses SEI growth, and likewise enhances cycling stability. This study provides theoretical guidance for the design of high performance lithium-ion batteries.

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