Hydrogen bonding and charge transport in a protic polymerized ionic liquid.

Hydrogen bonding and charge transport in the protic polymerized ionic liquid poly[tris(2-(2-methoxyethoxy)ethyl)ammoniumacryloxypropyl sulfonate] (PAAPS) are studied by combining Fourier transform infrared (FTIR) and broadband dielectric spectroscopy (BDS) in a wide temperature range from 170 to 300 K. While the former enables to determine precisely the formation of hydrogen bonds and other moiety-specific quantized vibrational states, the latter allows for recording the complex conductivity in a spectral range from 10-2 to 10+9 Hz. A pronounced thermal hysteresis is observed for the H-bond network formation in distinct contrast to the reversibility of the effective conductivity measured by BDS. On the basis of this finding and the fact that the conductivity changes with temperature by orders of magnitude, whereas the integrated absorbance of the N-H stretching vibration (being proportional to the number density of protons in the hydrogen bond network) changes only by a factor of 4, it is concluded that charge transport takes place predominantly due to hopping conduction assisted by glassy dynamics (dynamic glass transition assisted hopping) and is not significantly affected by the establishment of H-bonds.

Charge transport and glassy dynamics in polymeric ionic liquids as reflected by their inter- and intramolecular interactions.

Polymeric ionic liquids (PILs) form a novel class of materials in which the extraordinary properties of ionic liquids (ILs) are combined with the mechanical stability of polymeric systems qualifying them for multifold applications. In the present study broadband dielectric spectroscopy (BDS), Fourier transform infrared spectroscopy (FTIR), AC-chip calorimetry (ACC) and differential scanning calorimetry (DSC) are combined in order to unravel the interplay between charge transport and glassy dynamics. Three low molecular weight ILs and their polymeric correspondents are studied with systematic variations of anions and cations. For all examined samples charge transport takes place by glassy dynamics assisted hopping conduction. In contrast to low molecular weight ILs the thermal activation of DC conductivity for the polymeric systems changes from a Vogel-Fulcher-Tammann- to an Arrhenius-dependence at a (sample specific) temperature Tσ0. This temperature has been widely discussed to coincide with the glass transition temperature Tg, a refined analysis, instead, reveals Tσ0 of all PILs under study at up to 80 K higher values. In effect, below the Tσ0 charge transport in PILs becomes more efficient - albeit on a much lower level compared to the low molecular weight pendants - indicating conduction paths along the polymer chain. This is corroborated by analysing the temperature dependence of specific IR-active vibrations showing at Tσ0 distinct changes in the spectral position and the oscillator strength, whereas other molecular units are not affected. This leads to the identification of charge transport responsive (CTR) as well as charge transport irresponsive (CTI) moieties and paves the way to a refined molecular understanding of electrical conduction in PILs.