离子电池中SEI的电化学作用和电极表面修改的设计原则
Tamio Ikeshoji1,2, Seiichiro Ishino1, Toshihiro Kaneko1
1NISSAN ARC, Ltd., 1 Natsushima-cho, Yokosuka, Kanagawa 237-0061, Japan. t.ikeshoji@r5.dion.ne.jp.
Physical chemistry chemical physics : PCCP
|February 26, 2025
概括
石墨电极的表面修改显著影响离子电池的性能. 特定的表面群,如LiF集群或CHO群,对离子转移的激活能量较低,从而使充电速度更快.
科学领域:
- 电化学 电化学 电化学
- 材料科学 材料科学 材料科学
- 计算化学计算化学
背景情况:
- 固体电解质间相 (SEI) 对于离子电池的耐用性和电荷转移至关重要.
- 了解SEI形成及其对电极表面的影响,是开发高性能电池的关键.
研究的目的:
- 通过模拟表面修饰石墨电极,介绍大电流电池的设计原理.
- 研究表面形态对电荷转移反应动学的影响.
主要方法:
- 使用混合方法,结合第一原则 (密度函数理论) 和解决方案理论 (参考交互点方法).
- 模拟了各种表面修改的石墨电极,以确定+离子溶解/解溶的激活能量.
- 分析了表面形态和电荷转移激活能量之间的关系.
主要成果:
- 用LiF集群或CHO组进行表面修改,使电荷转移激活能量降低到~0.3 eV,而H端,LiF层或OH端石墨则降低到~0.6 eV.
- F集群和孤立的CHO群为+溶解提供了充足的3D空间,降低了激活能量.
- 平面 (H端,LiF层,OH端) 限制了溶解空间,从而导致更高的激活能量.
结论:
- 表面形态极大地影响了离子电池中的电荷转移动力学.
- 优化的表面修改,如LiF集群或CHO组,可以通过促进更快的离子转移来提高电池性能.
- 在修改的表面上,溶解/解溶和电荷转移之间的弱合导致阳极转移系数接近单位.
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