The development of high‐energy‐density Li metal batteries are hindered by electrolyte consumption and uneven lithium deposition due to the unstable lithium‐electrolyte interface (SEI). In this work, tetraglyme is introduced into ester electrolyte to regulate the Li⁺‐solvation structures for stable SEI while remaining appropriate voltage window for high‐voltage cathodes. In the modified solvation structures, an enhanced lowest unoccupied molecular orbital energy level occurs, resulting in relieved electrolyte degradation. In addition, the modified solvation structures can facilitate adequate LiNO₃ dissolution in the ester electrolyte (denoted as E‐LiNO₃), contributing to constant supplement of constructing highly conductive LiN_xO_y‐containing SEI for dendrite‐free Li deposition under high capacity condition. As a result, the Li||Cu cell‐based on this electrolyte exhibits high Li plating/stripping Coulombic efficiency of 98.2% over 350 cycles. Furthermore, when paired with high‐voltage LiNi_0.5Co_0.2Mn_0.3O₂ cathodes, the E‐LiNO₃ enables a stable cycling with a high‐energy‐density of 296 Wh kg⁻¹ based on the full cell under realistic testing conditions (lean electrolyte of 3 g Ah⁻¹, limited Li excess of 2.45‐fold, and high areal capacity of 4 mAh cm⁻²).

中文翻译：

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调节高能量密度锂金属电池酯电解质的Li +溶剂化结构

高能量密度锂金属电池的发展受到电解质消耗和锂-电解质界面（SEI）不稳定的不均匀锂沉积的阻碍。在这项工作中，将四甘醇二甲醚引入酯电解质中，以调节Li ⁺溶剂化结构，以实现稳定的SEI，同时为高压阴极保留适当的电压窗口。在改性的溶剂化结构中，发生了提高的最低未占据分子轨道能级，从而减轻了电解质的降解。此外，改性的溶剂化结构可促进LiNO ₃在酯电解质（称为E-LiNO ₃）中的充分溶解，有助于不断补充构造高导电性LiN _x O的方法。含_y的SEI，用于在高容量条件下进行无枝晶锂沉积。结果，基于这种电解质的Li || Cu电池在350个循环中显示98.2％的高Li镀/剥离库仑效率。此外，当与高压LiNi _0.5 Co _0.2 Mn _0.3 O ₂阴极搭配使用时，E-LiNO ₃可以在实际测试条件下以整个电池为基准，以296 Wh kg ^-1的高能量密度实现稳定的循环（ 3 g Ah ^-1的稀薄电解液，2.45倍的有限Li过量和4 mAh cm ^-2的高面容量。