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The in situ formation of LiF and Li3N nanocrystals, alongside Li dendrite deposition, was visually monitored by cryo-TEM, greatly aiding theoretical simulation and kinetic analysis of structural evolution during battery charge and discharge. In solid-state LiLiFePO4 and LiNCM-811 full cells, as well as in pouch cells, this membrane, featuring high thermal stability and robust mechanical strength, exhibited improved rate performance and exceptionally lo