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

Aggressive chemistry involving Li metal anode (LMA) and high-voltage LiNi(0.8)Mn(0.1)Co(0.1)O(2) (NCM811) cathode is deemed as a pragmatic approach to pursue the desperate 400 Wh kg(−1). 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(4) 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(2) cathode. Accordingly, industrial anode-free pouch cells under harsh testing conditions deliver a high energy of 442.5 Wh kg(−1) with 80% capacity retention after 100 cycles.