Journal ArticleEffect of Confinement on the Structure–Conductivity Relationship in PEO/LiTFSI Electrolytes in 3D Microporous ScaffoldsPathreeker, Shreyas; Koh, Hyeongjun; Kong, Weiwei; Robinson, Richard; Weissman, Gillian; Stach, Eric A; Detsi, Eric; Composto, Russell JBecause 3D batteries comprise solid polymer electrolytes (SPE) confined to high surface area porous scaffolds, the interplay between polymer confinement and interfacial interactions on total ionic conductivity must be understood. This paper investigates contributions to the structure-conductivity relationship in poly(ethylene oxide) (PEO)–lithium bis(trifluorosulfonylimide) (LiTFSI) complexes confined to microporous nickel scaffolds. For bulk and confined conditions, PEO crystallinity decreases as the salt concentration (Li+:EO (r) = 0.0.125, 0.0167, 0.025, 0.05) increases. For pure PEO and all r values except 0.05, PEO crystallinity under confinement is lower than in the bulk, whereas glass transition temperature remains statistically invariant. At 298 K (semicrystalline), total ionic conductivity under confinement is higher than in the bulk at r = 0.0167, but remains invariant at r = 0.05; however, at 350 K (amorphous), total ionic conductivity is higher than in the bulk for both salt concentrations. Time–of–flight secondary ion mass spectrometry indicates selective migration of ions towards the polymer–scaffold interface. In summary, for the 3D structure studied, polymer crystallinity, interfacial segregation, and tortuosity play an important role in determining total ionic conductivity and, ultimately, the emergence of 3D SPEs as energy storage materials.ACS2024-11-0410554965ACS Macro Letters131577 to 15832161-1653https://doi.org/10.1021/acsmacrolett.4c005551905912; 2407300microporous, polymer composite, structure-conductivityNational Science Foundation