摘要： Poly(ethylene 3,4-dioxythiophene (PEDOT) ?lms synthesized by oxidative chemical vapor deposition (oCVD) display strong electrochemical activity in the region from 2 to 4.2 V vs Li/Li+. By contrast, the more commonly studied PEDOT:polystyrenesulfonate (PSS) ?lms have negligible electrochemical activity in this region. For the oCVD ?lms, its small dopant anions (Cl?) that can easily enter and exit the polymer structure allow exchange with the Li+ counterion in solution, while for PEDOT:PSS, the poly(styrenesulfonate) dopant is a large macromolecule having substantially lower mobility. Here, we seek to elucidate the relationship between the structural characteristics of oCVD PEDOT thin ?lms and their electrochemical properties, particularly in Li-ion electrolyte systems. Speci?cally, we seek to rationally design the thin-?lm properties of oCVD PEDOT for high-rate performance and cycle life by varying the ?lm growth temperature. We observe that the dominant e?ect of increasing growth temperature is an in situ reorganization to an edge-on ?lm texture. In this case, the π?π stack is perpendicular to the substrate surface. The alternative dominant texture is face-on dominance, where the π?π stack is parallel to the substrate surface. For the ?rst time, we show that edge-on dominant ?lms provide higher speci?c capacities for a given charge/discharge rate. Furthermore, Raman spectroscopy demonstrates that edge-on dominant ?lms are less susceptible to oxidative damage after long-term cycling. This also enables edge-on dominant ?lms to maintain lower charge-transfer resistances compared to identically cycled face-on ?lms. Edge-on oCVD PEDOT is paired with molybdenum disul?de to demonstrate thick, optimized oCVD PEDOT thin ?lms in asymmetric devices for high-rate electrochemical energy storage.