Engineering the Solid–Electrolyte Interphase via NO 3 − Coordination at Open Metal Sites in HKUST‐1 for Stable Lithium Metal Anodes

ABSTRACT Metal‐organic frameworks (MOFs) are promising hosts for quasi‐solid electrolytes (QSEs) by integrating liquid electrolytes (MOF@LE QSEs), yet stabilizing lithium metal anodes (LMAs) to enhance electrochemical performance remains a challenge. Here, we introduce a strategy leveraging open metal sites (OMSs) in HKUST‐1 (Cu 3 (BTC) 2 ) combined with LiNO 3 to tailor solid electrolyte interphase (SEI) chemistry and lithium deposition. OMSs in HKUST‐1 anchor NO 3 − and promote LiNO 3 dissociation, enriching SEI with nitrogen‐containing inorganic compounds and enabling uniform and spherical lithium morphology. Consequently, LMAs with LiNO 3 ‐incorporated HKUST‐1 membrane QSE (HM‐LN QSE) achieve a critical current density of 2.7 mA cm −2 , with stable lithium plating/stripping over 650 h at 0.2 mA cm −2 and more than 300 h at 0.5 mA cm −2 . Moreover, LiLiFePO 4 cells assembled with HM‐LN QSEs delivere a discharge capacity of 81.2 mAh g −1 at 5 C and retain 81.2% capacity after 350 cycles at 2 C, demonstrating superior electrochemical stability and performance. This innovative MOF‐based approach significantly enhances SEI stability and LMA performance, advancing lithium metal battery technology.