Characterization of the structure and chemistry of the solid-electrolyte interface by cryo-EM leads to...

Solid-state lithium-metal (Li⁰) batteries are gaining traction for electric vehicle applications because they replace flammable liquid electrolytes with a safer, solid-form electrolyte that also offers higher energy density and better resistance against Li dendrite formation. Solid polymer electrolytes (SPEs) are highly promising candidates because of their tuneable mechanical properties and easy manufacturability; however, their electrochemical instability against lithium-metal (Li⁰), mediocre conductivity and poorly understood Li⁰/SPE interphases have prevented extensive application in real batteries. In particular, the origin of the low Coulombic efficiency (CE) associated with SPEs remains elusive, as the debate continues as to whether it originates from unfavoured interfacial reactions or lithium dendritic growth and dead lithium formation. In this work, we use state-of-the-art cryo-EM imaging and spectroscopic techniques to characterize the structure and chemistry of the interface between Li⁰ and a polyacrylate-based SPE. Contradicting the conventional knowledge, we find that no protective interphase forms, owing to the sustained reactions between deposited Li dendrites and polyacrylic backbones and succinonitrile plasticizer. Due to the reaction-induced volume change, large amounts of cracks form inside the Li dendrites with a stress-corrosion-cracking behaviour, indicating that Li⁰ cannot be passivated in this SPE system. On the basis of this observation, we then introduce additive engineering, leveraging from knowledge of liquid electrolytes, and demonstrate that the Li⁰ surface can be effectively protected against corrosion using fluoroethylene carbonate, leading to densely packed Li⁰ domes with conformal and stable solid-electrolyte interphase films. Owing to the high room-temperature ionic conductivity of 1.01 mS cm^-1, the high transference number of 0.57 and the stabilized lithium-electrolyte interface, this improved SPE delivers an excellent lithium plating/stripping CE of 99% and 1,800 hours of stable cycling in Li||Li symmetric cells (0.2 mA cm^-2, 1 mAh cm^-2). This improved cathodic stability, along with the high anodic stability, enables a record high cycle life of >2,000 cycles for Li||LiFePO₄ and >400 cycles for Li||LiCoO₂ full cells.