Adv Polym Sci (2014) 255: 97–138
DOI: 10.1007/12_2012_203
# Springer-Verlag Berlin Heidelberg 2013
Published online: 15 June 2013
Ion Conduction in Solid Polyelectrolyte
Complex Materials
Cornelia Cramer and Monika Scho ¨nhoff
Abstract This chapter describes the progress made in understanding the mechanisms
of ion conduction in polyelectrolyte complexes (PEC). Understanding of ion
dynamics is based on frequency-dependent conductivity data obtained by impedance
spectroscopy as a function of temperature, hydration, and composition. In most of the
work, strong polyelectrolytes such as poly(alkali 4-styrene sulfonate) (AlkaliPSS) and
poly(diallyldimethyl ammoniumchloride) (PDADMAC) are employed, forming
complexes of type xAlkaliPSS · (1 À x) PDADMAC. The dc conductivity is always
determined by the alkali ions, which exhibit a size-dependent mobility. This holds
even in PEC with an excess of PDADMAC. The ion dynamics and transport
mechanisms are different in PDADMAC-rich and in NaPSS-rich PEC. We review
the treatment of the frequency-dependent shape of conductivity spectra by scaling
concepts and by models involving forward–backward hopping motions of small ions
as well as localized motions of charges. Thus, many quantitative concepts established
in other disordered ion conductors can be transferred to PEC. In addition to the
well-known time–temperature superposition principle (TTSP), the novel concept of
time–humidity superposition (THSP) was established for PEC and describes the
dependence of ion dynamics on water content.
Keywords Dielectric spectroscopy Á Electrolyte Á Impedance spectroscopy Á Ion
conductor Á Ion dynamics Á Polyelectrolyte complex
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
2 Conductivity Spectra: Concepts and Initial Findings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
C. Cramer and M. Scho ¨nhoff (*)
Institute of Physical Chemistry, University of Muenster, Correnstraße 28/30, 48149 Mu ¨nster,
Germany
e-mail: cramerc@uni-muenster.de; schonhoff@uni-muenster.de
DOI: 10.1007/12_2012_203
# Springer-Verlag Berlin Heidelberg 2013
Published online: 15 June 2013
Ion Conduction in Solid Polyelectrolyte
Complex Materials
Cornelia Cramer and Monika Scho ¨nhoff
Abstract This chapter describes the progress made in understanding the mechanisms
of ion conduction in polyelectrolyte complexes (PEC). Understanding of ion
dynamics is based on frequency-dependent conductivity data obtained by impedance
spectroscopy as a function of temperature, hydration, and composition. In most of the
work, strong polyelectrolytes such as poly(alkali 4-styrene sulfonate) (AlkaliPSS) and
poly(diallyldimethyl ammoniumchloride) (PDADMAC) are employed, forming
complexes of type xAlkaliPSS · (1 À x) PDADMAC. The dc conductivity is always
determined by the alkali ions, which exhibit a size-dependent mobility. This holds
even in PEC with an excess of PDADMAC. The ion dynamics and transport
mechanisms are different in PDADMAC-rich and in NaPSS-rich PEC. We review
the treatment of the frequency-dependent shape of conductivity spectra by scaling
concepts and by models involving forward–backward hopping motions of small ions
as well as localized motions of charges. Thus, many quantitative concepts established
in other disordered ion conductors can be transferred to PEC. In addition to the
well-known time–temperature superposition principle (TTSP), the novel concept of
time–humidity superposition (THSP) was established for PEC and describes the
dependence of ion dynamics on water content.
Keywords Dielectric spectroscopy Á Electrolyte Á Impedance spectroscopy Á Ion
conductor Á Ion dynamics Á Polyelectrolyte complex
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
2 Conductivity Spectra: Concepts and Initial Findings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
C. Cramer and M. Scho ¨nhoff (*)
Institute of Physical Chemistry, University of Muenster, Correnstraße 28/30, 48149 Mu ¨nster,
Germany
e-mail: cramerc@uni-muenster.de; schonhoff@uni-muenster.de