Improving Ionic Conformality Across Polymer Electrolyte|Electrode Interfaces.

Abstract

Maintaining uniform ionic transport at electrode|electrolyte interfaces, i.e., ionic conformality, remains challenging in polymer electrolyte (PE)-based solid-state batteries. Morphological conformality does not necessarily imply ionic conformality. In PEs, which typically consist of a mechanically supporting component and distinct ionically conductive components, the rearrangement or depletion of mobile ion-conductive domains at interfaces can disrupt ionic transport pathways. Such localized ionic depletion contributes to interfacial instability and capacity degradation in high-voltage lithium-metal batteries. Herein, an electrolyte design approach aimed at minimizing interfacial heterogeneities is demonstrated through compositional adjustments, characterized by spatially resolved structural and chemical X-ray techniques and NMR diffusometry to elucidate ion transport dynamics. This approach improves ionic conformality at electrode interfaces, enhancing cycling stability in Li||LiNi₀.₈Co₀.₁Mn₀.₁O₂ (NMC811) coin and pouch cells cycled at high voltages. These results contribute to understanding interfacial behaviors in multiphase PEs and inform strategies for improving stability across solid-state battery interfaces.