Abstract
Nanoconfined/sub-nanoconfined solvent molecules tend to undergo dramatic changes in their properties and behaviours. In this work, we find that unlike typical bulk liquid electrolytes, electrolytes confined in a sub-nanoscale environment (inside channels of a 6.5 Å metal-organic framework, defined as a quasi-solid electrolyte) exhibits unusual properties and behaviours: higher boiling points, highly aggregated configurations, decent lithium-ion conductivities, extended electrochemical voltage windows (approximately 5.4 volts versus Li/Li+) and nonflammability at high temperatures. We incorporate this interesting electrolyte into lithium-metal batteries (LMBs) and find that LMBs cycled in the quasi-solid electrolyte demonstrate an electrolyte interphase-free (CEI-free) cathode and dendrite-free Li-metal surface. Moreover, high-voltage LiNi0.8Co0.1Mn0.1O2//Li (NCM-811//Li with a high NCM-811 mass loading of 20 mg cm-2) pouch cells assemble with the quasi-solid electrolyte deliver highly stable electrochemical performances even at a high working temperature of 90 °C (171 mAh g-1 after 300 cycles, 89% capacity retention; 164 mAh g-1 after 100 cycles even after being damaged). This strategy for fabricating nonflammable and ultrastable quasi-solid electrolytes is promising for the development of safe and high-energy-density LIBs/LMBs for powering electronic devices under various practical working conditions.