Anion-enrichment interface enables high-voltage anode-free lithium metal batteries.

Mao, Minglei; Ji, Xiao; Wang, Qiyu; Lin, Zejing; Li, Meiying; Liu, Tao; Wang, Chengliang; Hu, Yong-Sheng et al. · Nat Commun · 2023

basic_science · Level V

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Abstract

Aggressive chemistry involving Li metal anode (LMA) and high-voltage LiNi<sub>0.8</sub>Mn<sub>0.1</sub>Co<sub>0.1</sub>O<sub>2</sub> (NCM811) cathode is deemed as a pragmatic approach to pursue the desperate 400 Wh kg<sup>-1</sup>. Yet, their implementation is plagued by low Coulombic efficiency and inferior cycling stability. Herein, we propose an optimally fluorinated linear carboxylic ester (ethyl 3,3,3-trifluoropropanoate, FEP) paired with weakly solvating fluoroethylene carbonate and dissociated lithium salts (LiBF<sub>4</sub> and LiDFOB) to prepare a weakly solvating and dissociated electrolyte. An anion-enrichment interface prompts more anions' decomposition in the inner Helmholtz plane and higher reduction potential of anions. Consequently, the anion-derived interface chemistry contributes to the compact and columnar-structure Li deposits with a high CE of 98.7% and stable cycling of 4.6 V NCM811 and LiCoO<sub>2</sub> cathode. Accordingly, industrial anode-free pouch cells under harsh testing conditions deliver a high energy of 442.5 Wh kg<sup>-1</sup> with 80% capacity retention after 100 cycles.