Rational design of advanced electrolytes to improve the high‐voltage capability has been attracting wide attention as one critical solution to enable next‐generation high‐energy‐density batteries. However, the limited understanding of electrolyte antioxidant chemistry as well as the lack of valid quantization approaches have resulted in knowledge gap, which hinders the formulation of new electrolytes. Herein, we construct a standard curve based on representative solvation structures to quantify the oxidation stability of ether‐based electrolytes, which reveals the linear correlation between the oxidation potential and the atomic charge of the least oxidation‐resistant solvent. Dictating by the regularity between solvation composition and oxidation potential, a (Trifluoromethyl)cyclohexane‐based localized high‐concentration electrolyte dominated by anion‐less solvation structures was designed to optimize the cycling performance of 4.5 V 30‐μm‐Li||3.8‐mAh cm‐2‐LiCoO2 batteries, which maintained 80% capacity retention even after 440 cycles. The consistency of experimental and computational results validates the proposed principles, offering a fundamental guideline to evaluate and design aggressive electrochemical systems.

中文翻译：

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通过构建电位标度关系升级电解质抗氧化化学

作为实现下一代高能量密度电池的关键解决方案之一，合理设计先进电解质以提高高电压能力已引起广泛关注。然而，对电解质抗氧化化学的了解有限以及缺乏有效的量化方法导致了知识差距，这阻碍了新电解质的配制。在此，我们基于代表性溶剂化结构构建了标准曲线来量化醚基电解质的氧化稳定性，该曲线揭示了氧化电位与最不抗氧化溶剂的原子电荷之间的线性相关性。根据溶剂化组成和氧化电位之间的规律性，设计了一种以无阴离子溶剂化结构为主的(三氟甲基)环己烷基局部高浓度电解质，以优化4.5 V 30-μm-Li||3.8-mAh的循环性能cm-2-LiCoO2电池，即使在440次循环后仍保持80%的容量保持率。实验和计算结果的一致性验证了所提出的原理，为评估和设计侵蚀性电化学系统提供了基本指导。