Block copolymer/ionic liquid films: The effect of ionic liquid composition on morphology and ion conduction

The effect of morphology on ion transport in ionic liquid-based solid-state films was investigated. In this study, mixtures of a block copolymer, poly(styrene-b-methyl methacrylate) (SbMMA), and an ionic liquid (IL), 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl)imide (EMIm-TFSI), were prepared as clear solid-state films at various IL compositions (0-50 wt%) by solution casting from a volatile co-solvent. The IL was preferentially miscible with the MMA block as evidenced by visual inspection and differential scanning calorimetry. Both equilibrium and non-equilibrium morphologies were identified with X-ray scattering and transmission electron microscopy and the morphology varied with MMA/IL volume fraction. The morphology and microdomain orientation had a significant impact on ionic conductivity. Higher through-plane conductivities were observed in morphologies with a three-dimensionally continuous conducting path (e.g., non-conducting S cylinders) compared to morphologies with a non-continuous conducting path (e.g., lamellae). When the lamellae were oriented in the plane, the through-plane conductivity was significantly lower than the in-plane conductivity, while the conductivity was direction-independent when the morphologies have a continuous conductive path. Also, a significant increase in conductivity was observed with increasing IL content at the glass transition of the conductive (MMA/IL) microdomain. Finally, significantly higher ionic conductivities can be achieved in a block copolymer/IL solid-state film compared to a homopolymer/IL film at the same IL content (wt%), because the non-conductive microdomain excludes IL, which produces a higher local IL concentration in the conductive phase.