Liu Zeyuan, Zhang Shuoqing, Zhang Haikuo, Ma Baochen, Zhu Haotian, Zhou Tao, Li Long, Xiao Xuezhang, Li Ruhong, Chen Lixin, Deng Tao, Fan Xiulin
State Key Laboratory of Silicon and Advanced Semiconductor Materials, School of Materials Science and Engineering, Zhejiang University, Hangzhou, 310027, China.
China-UK Low Carbon College, Shanghai Jiao Tong University, Shanghai, 201306, China.
Angew Chem Int Ed Engl. 2025 Jul 28;64(31):e202506395. doi: 10.1002/anie.202506395. Epub 2025 Jun 10.
The long-lasting stability of high-voltage lithium metal batteries (LMBs) critically rely on both the cathodic and anodic stability of electrolytes, which can be enhanced by increasing the salt-to-solvent molar ratio. However, this approach is limited by solubility constraints. In this work, we introduce a dual-anchoring strategy to regulate the solvating sites of glymes via directional atomic interactions. Specifically, F-H interactions transform the Li-glyme coordination and induce more anion coordination within Li primary solvation sheath, whereas H-O interactions reduce the electron density at free oxygen sites, thus raising the oxidational potential of glyme and enhancing the overall oxidation stability of electrolytes. This strategy results in an electrolyte with exceptional compatibility with both lithium metal anode (LMA) and high-voltage cathode, enabling LMA with an ultrahigh coulombic efficiency (CE) of 99.76%. Furthermore, the assembled LMBs exhibit extended lifespans, retaining 80% of their capacity under aggressive conditions: 834 and 370 cycles at 4.4 and 4.5 V, respectively, for 30-µm-Li||2.0-mAh cm LiNiCoMnO cells and 100 cycles for anode-free Cu||LiNiCoMnO pouch cells. This work offers novel insights into the advancement of next-generation LMBs based on ether-based electrolytes.
高压锂金属电池（LMBs）的长期稳定性严重依赖于电解质的阴极和阳极稳定性，通过提高盐与溶剂的摩尔比可以增强这种稳定性。然而，这种方法受到溶解度限制。在这项工作中，我们引入了一种双锚定策略，通过定向原子相互作用来调节甘醇二甲醚的溶剂化位点。具体而言，F-H相互作用改变了Li-甘醇二甲醚配位，并在Li初级溶剂化鞘层内诱导更多的阴离子配位，而H-O相互作用降低了游离氧位点的电子密度，从而提高了甘醇二甲醚的氧化电位并增强了电解质的整体氧化稳定性。这种策略产生了一种与锂金属阳极（LMA）和高压阴极都具有优异兼容性的电解质，使LMA具有99.76%的超高库仑效率（CE）。此外，组装的LMBs表现出延长的寿命，在苛刻条件下保持其容量的80%：对于30-µm-Li||2.0-mAh cm LiNiCoMnO电池，在4.4和4.5 V下分别循环834次和370次，对于无阳极的Cu||LiNiCoMnO软包电池循环100次。这项工作为基于醚基电解质的下一代LMBs的发展提供了新的见解。
