Molecular Probes Reveal Chemical Selectivity of the Solid–Electrolyte Interphase
Molecular Probes Reveal Chemical Selectivity of the Solid–Electrolyte Interphase
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DOI：
10.1021/acs.jpcc.8b06564
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发表时间：
2018-08
期刊：
影响因子：
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通讯作者：
Oliver C. Harris;Maureen H. Tang
中科院分区：
文献类型：
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作者：
Oliver C. Harris;Maureen H. Tang
众所周知，固体电解质界面（SEI）在非水电池的强还原性负极和有机电解质之间提供关键保护。具有不良钝化SEI的电池将遭受快速容量衰减和短寿命。尽管其重要性和广泛的研究，其结构和组成，SEI钝化的机制仍然知之甚少。在这项工作中，我们证明了使用电化学收集发电机测量的SEI是化学选择性的钝化，并提出了一个模型的基础上，催化活性位点来解释其性能。用官能化二茂铁介体对SEI进行电化学询问表明，透膜介体还原对介体官能团比尺寸更敏感，这表明优先分配到有机SEI层中。控制电极串扰的其他实验表明，溶解的过渡金属的掺入增加…
The solid–electrolyte interphase (SEI) is well-known to provide critical protection between the strongly reducing negative electrode and the organic electrolytes of nonaqueous batteries. Batteries with a poorly passivating SEI will suffer from rapid capacity fade and short lifetimes. Despite its importance and extensive study of its structure and composition, the mechanism of SEI passivation remains poorly understood. In this work, we demonstrate using electrochemical collector-generator measurements that the SEI is chemically selective in its passivation and propose a model based on catalytic active sites to explain its performance. Electrochemically interrogating the SEI with functionalized ferrocene mediators shows that the through-film mediator reduction is much more sensitive to mediator functional group than size, indicating preferential partitioning into the organic SEI layer. Additional experiments with controlled electrode crosstalk show that incorporation of dissolved transition metals increases...