The morphology and size of the discharge products in Na−O₂ batteries are largely dominated by the interactions of the electrolyte with superoxide and sodium ions; therefore, an in‐depth understanding is essential for achieving high performance batteries. Herein, we report a framework designed to understand solvation and coordination in the recently discovered hybrid electrolytes, based on glyme and a pyrrolidinium ionic liquid. FTIR and NMR spectroscopic techniques, coupled with molecular dynamics simulations, have been used to characterize these systems. We demonstrate that the presence of ionic liquid in the hybrid electrolyte affects the superoxide coordination environment by weakening the glyme‐Na⁺ interactions, and generating solvent separated ion pairs. All these factors lead to different deposition mechanisms, which will determine the battery performance. The Na⁺ solvation shell compositions, anion conformers and relative free glyme content are also evaluated. The combinatorial approach used in this study‐experimental and computational – can be applied for further design of these hybrid electrolytes and other metal – O₂ chemistries and electrochemical systems.

中文翻译：

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揭示形态在Na-O2电池的Glyme：离子液体混合电解质中的作用

Na-O ₂电池中放电产物的形态和大小在很大程度上由电解质与超氧化物和钠离子的相互作用所决定。因此，深入了解对于获得高性能电池至关重要。本文中，我们报告了一个框架，该框架旨在了解基于甘醇二甲醚和吡咯烷鎓离子液体的最近发现的混合电解质中的溶剂化和配位。FTIR和NMR光谱技术以及分子动力学模拟已被用来表征这些系统。我们证明了混合电解质中离子液体的存在会通过削弱glyme-Na ^+来影响超氧化物配位环境。相互作用，并生成溶剂分离的离子对。所有这些因素导致了不同的沉积机制，这将决定电池的性能。还评估了Na ⁺溶剂化壳的组成，阴离子构象剂和相对游离甘醇二甲醚的含量。本研究中使用的组合方法-实验和计算-可以用于这些杂化电解质和其他金属-O ₂化学和电化学系统的进一步设计。