Electrochemical Activation of Ordered Mesoporous Solid Electrolyte Interphases to Enable Ultra‐Stable Lithium Metal Batteries

Abstract In Li metal batteries, the rational construction of artificial solid electrolyte interphase (ASEI) can homogenize the Li‐ion flowing and Li‐mass plating/stripping, and reinforce the mechanical and electrochemical stabilities of electrode–electrolyte interface. Here, an ordered‐mesoporous powder zirconium oxophosphate (ZrOP) is proposed to construct a Li‐ion conductive ASEI by brushing ZrOP on metallic Li. The P‐induced amorphization in ZrOP is expected to accelerate the spontaneous lithiation reaction and promote the generation of P‐contained Li‐ion conductors and LiF domains in ASEI during Li anode cycling. The electrochemical activation of ASEI with promoted ionic conductivity and interconnected porous network is favorable for the homogeneous nucleation and growth of Li metal grains (with ≈10 µm in size), and the suppression of Li dendrites and volume expansion during long‐term Li plating and stripping. The ZrOP‐modified Li symmetric cell enables a long lifespan of over 1600 h at 1 mA cm⁻², and the corresponding LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) based full cell displays a stable cycling for at least 300 cycles with a capacity retention of 80% at 1 C. The modified thin Li foil (40 µm in thickness) anode also enables a multilayered pouch cell based on a high‐loading NCM811 cathode with stable cycling and reversible capacity over 1 Ah.