Ref HAL: hal-03131544_v1
DOI: 10.1021/acs.jpcb.0c07549
WoS: WOS:000592964600024
Exporter : BibTex | endNote
Résumé:

Polymerized ionic liquids (PolyILs) are promising candidates for a broad range of technologies. However, the relatively low conductivity of PolyILs at room temperature has strongly limited their applications. In this work, we provide new insights into the roles of various microscopic parameters controlling ion transport in these polymers, which are crucial for their rational design and practical applications. Using broadband dielectric spectroscopy and neutron and light scattering techniques, we found a clear connection between the activation energy for conductivity, fast dynamics, and high-frequency shear modulus in PolyILs at their glass transition temperature (Tg). In particular, our analysis reveals a correlation between conductivity and the amplitude of fast picosecond fluctuations at Tg, suggesting the possible involvement of fast dynamics in lowering the energy barrier for ion conductivity. We also demonstrate that both the activation energy for ion transport and the amplitude of the fast fluctuations depend on the high-frequency shear moduli of PolyILs, thus identifying a practically important parameter for tuning conductivity. The parameters recognized in this work and their connection to the ionic conductivity of PolyILs set the stage for a deeper understanding of the mechanism of ion transport in PolyILs in the glassy state.