Ion Association and Electrolyte Structure at Surface Films in Lithium-Ion Batteries
Ion Association and Electrolyte Structure at Surface Films in Lithium-Ion Batteries
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锂离子电池表面膜的离子缔合和电解质结构
DOI：
10.1021/acs.jpcc.1c00393
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Jorn, Ryan
中科院分区：
文献类型：
--
作者：
Pinca, Justin R.;Duborg, William G.;Jorn, Ryan
在锂离子电池充放电过程中，碳酸盐电解质因氧化还原副反应而降解，从而产生电极表面膜。这些膜的组成取决于电极表面处的电解质层的组成和其中发现的离子溶剂化壳的结构。然而，在界面处的电解质的组成和结构可以显著地不同于它们在本体中的对应物，如先前在空气和矿物表面所报道的。因此，循环关系成立，其中形成的表面膜取决于电解质结构，电解质结构又受到表面膜存在的影响。在这项工作中，从固体界面上的碳酸盐电解质的影响被认为是：离子积累，离子配对，和溶剂交换动力学。通过考虑这些影响在四个不同的表面不同的溶剂亲和力（LiF，Li 2CO 3，Li 2 EDC，和石墨），我们探讨这些界面行为的溶剂-表面相互作用和离子-表面相互作用的影响。经典的分子动力学提供了一种途径来探索在电解质边界的分子结构，和两种不同的电解质被认为是调查的积累，配对和动力学的离子缔合的作用。通过考虑的变化，作为一个电解质之间切换的结果，主要是溶剂分离的离子与另一个接触离子对，我们提供的证据表明，无论是散装离子协会和溶剂-表面相互作用的离子聚集在电极表面的关键描述符。从这些模拟的见解通知不仅对周围的电解质电池接口的影响，但也在这些接口的经典分子动力学模拟之间的差异的起源。
During lithium-ion battery charging and discharging, carbonate electrolytes degrade from redox side reactions to produce electrode surface films. The composition of these films depends on the composition of the electrolyte layer at the electrode surface and the structure of the ion solvation shells found therein. However, both the composition and structure of an electrolyte at an interface can vary significantly from their counterparts in the bulk, as reported previously at air and mineral surfaces. Hence, a circular relationship holds in which the surface films formed depend on the electrolyte structure, which in turn is impacted by the presence of the surface film. In this work, three impacts from solid interfaces on carbonate electrolytes are considered: ion accumulation, ion pairing, and solvent exchange dynamics. By considering these effects at four different surfaces of varying solvent affinities (LiF, Li2CO3, Li2EDC, and graphite), we explore the impact of solvent–surface interactions and ion–surface interactions on these interfacial behaviors. Classical molecular dynamics provides a route to explore the molecular structure at the electrolyte boundary, and two different electrolytes are considered to investigate the role of ion association on the accumulation, pairing, and dynamics. By considering the changes as a result of switching between one electrolyte with mostly solvent-separated ions to another with contact ion pairs, we provide evidence that both bulk ion association and the solvent–surface interaction are key descriptors of ion aggregation at the electrode surface. The insights from these simulations inform not only about the impacts of battery interfaces on the surrounding electrolyte but also on the origins of differences reported between classical molecular dynamics simulations at these interfaces.
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DOI：
10.1007/s41061-018-0187-2
发表时间：
2018-02-12
期刊：
Topics in current chemistry (Cham)
影响因子：
--
作者：
Chaudhari MI;Muralidharan A;Pratt LR;Rempe SB
通讯作者：
Rempe SB
影响因子：
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作者：
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影响因子：
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作者：
Yanbin Wang;Shayandev Sinha;P. R. Desai;Haoyuan Jing;Siddhartha Das
通讯作者：
Siddhartha Das
影响因子：
16.6
作者：
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Cheng Zhan;M. Ceron;S. Hawks;M. Otani;B. Wood;T. Pham;M. Stadermann;P. Campbell
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DOI：
--
发表时间：
2016
期刊：
影响因子：
--
作者：
J. D. Smith;S. Rick
通讯作者：
S. Rick