Ten times of LiNO3 solubility increase in co-solvents free ester-based carbonate electrolytes enables 450 Wh/kg lithium metal batteries

作者：Zhuijun Xu, Meilan Peng, Guangjiu Pan, Tianle Zheng, Yiyao Xiao, Weiping Xie, Yinghui Li, Jie Gao, Shanshan Yin, Qing Ji, Baohu Wu, Yi Miao, Siqi Shi, Ya‐Jun Cheng, Yonggao Xia, Peter Müller‐Buschbaum · 发表于：Energy storage materials · 年份：2025 · DOI：10.1016/j.ensm.2025.104779 · 被引用次数：4 · 研究领域：Advanced Battery Materials and Technologies、Advancements in Battery Materials、Thermal Expansion and Ionic Conductivity

• A two-step method dissolves 0.1 M LiNO 3 into carbonate ester-based electrolytes. • MD simulation: negative enthalpy drives LiNO 3 dissolution without co-solvents. • Performance boost is exhibited in Li||Cu, Li||Li, Li||LiNi 0.83 Mn 0.06 Co 0.11 O 2 coin cells. • A pouch cell with 450 Wh kg -1 is fabricated. • Solvation structure–SEI/CEI–performance correlation is studied. LiNO 3 is a promising additive for high-energy-density lithium metal batteries (LMBs) via regulating the solid electrolyte interphase (SEI) layer. However, the extremely low solubility of LiNO 3 in carbonate ester-based electrolytes limits applications. In this study, a two-step physical method successfully dissolves 0.1 M LiNO 3 into carbonate ester-based electrolytes without co-solvents (∼10 × higher solubility than conventional systems), where EC disrupts Li⁺–NO 3 ⁻ interactions and the subsequent mixing with a preformed LiFSI/LiPF 6 –DMC/FEC electrolyte releases part of the coordinated species, increasing entropy, while the remaining solvents/anions stabilize Li⁺ - making the process both enthalpically and entropically favorable. This facile, scalable, cost-effective way is confirmed by theoretical simulation and experimental investigations. With the synergistic effect of 4-fluoro-1,3-dioxolan-2-one (FEC), the NO 3 - anions preferentially enter the Li + solvation layer. Therefore, the enhanced SEI layer with LiF, Li x C, and Li 2 O homogenizes lithium deposition. The robust cathode–electrolyte interph...