An Intrinsically Nonflammable Electrolyte for Prominent‐Safety Lithium Metal Batteries with High Energy Density and Cycling Stability

Abstract Nex‐generation high‐energy‐density storage battery, assembled with lithium (Li)‐metal anode and nickel‐rich cathode, puts forward urgent demand for advanced electrolytes that simultaneously possess high security, wide electrochemical window, and good compatibility with electrode materials. Herein an intrinsically nonflammable electrolyte is designed by using 1 M lithium difluoro(oxalato)borate (LiDFOB) in triethyl phosphate (TEP) and N‐methyl‐N‐propyl‐pyrrolidinium bis(trifluoromethylsulfonyl)imide [Pyr₁₃][TFSI] ionic liquid (IL) solvents. The introduction of IL can bring plentiful organic cations and anions, which provides a cation shielding effect and regulates the Li⁺ solvation structure with plentiful Li⁺‐DFOB⁻ and Li⁺‐TFSI⁻ complexes. The unique Li⁺ solvation structure can induce stable anion‐derived electrolyte/electrode interphases, which effectively inhibit Li dendrite growth and suppress side reactions between TEP and electrodes. Therefore, the LiNi_0.9Co_0.05Mn_0.05O₂ (NCM90)/Li coin cell with this electrolyte can deliver stable cycling even under 4.5 V and 60 °C. Moreover, a Li‐metal battery with thick NCM90 cathode (≈ 15 mg cm⁻²) and thin Li‐metal anode (≈ 50 µm) (N/P ≈ 3), also reveals stable cycling performance under 4.4 V. And a 2.2 Ah NCM90/Li pouch cell can simultaneously possess prominent safety with stably passing the nail penetration test, and high gravimetric energy density of 470 Wh kg⁻¹ at 4.4 V.