A Stable Polymer‐based Solid‐State Lithium Metal Battery and its Interfacial Characteristics Revealed by Cryogenic Transmission Electron Microscopy

Abstract Solid‐state lithium metal batteries (SSLMBs) are a promising candidate for next‐generation energy storage systems due to their intrinsic safety and high energy density. However, they still suffer from poor interfacial stability, which can incur high interfacial resistance and insufficient cycle lifespan. Herein, a novel poly(vinylidene fluoride‑hexafuoropropylene)‐based polymer electrolyte (PPE) with LiBF 4 and propylene carbonate plasticizer is developed, which has a high room‐temperature ionic conductivity up to 1.15 × 10 −3 S cm −1 and excellent interfacial stability. Benefitting from the stable interphase, the PPE‐based symmetric cell can operate for over 1000 h. By virtue of cryogenic transmission electron microscopy (Cryo‐TEM) characterization, the high interfacial compatibility between Li metal anode and PPE is revealed. The solid electrolyte interphase is made up of an amorphous outer layer that can keep intimate contact with PPE and an inner Li 2 O‐dominated layer that can protect Li from continuous side reactions during battery cycling. A LiF‐rich transition layer is also discovered in the region of PPE close to Li metal anode. The feasibility of investigating interphases in polymer‐based solid‐state batteries via Cryo‐TEM techniques is demonstrated, which can be widely employed in future to rationalize the correlation between solid‐state electrolytes and battery performance from ultrafine interfacial structures.