Ion‐matrix coupling in polymer electrolytes from relaxation time studies

We review the effects of temperature on conductance and viscosity in the liquid state of vitreous ionic conductors and show how differences may be best understood by comparison of relaxation times for electrical and mechanical stresses acting on liquid or glassy states of the material. This leads to the definition of a conductivity/viscosity mode decoupling index , useful as a figure of merit for the solid electrolyte. In applying the same approach to polymer electrolyte systems a problem is encountered due to the molecular weight dependence of the viscosity. This is resolved by deriving a ‘monomer’ shear relaxation time for the polymer electrolyte solution and showing that this quantity corresponds closely with the ‘local’ mechanical relaxation time obtained from light scattering studies (which is a molecular weight independent quantity for pure polypropylene oxide and other polymers of low T g ). Comparison of the electrical relaxation times of the polymer solution with the ‘local’ (or ‘matrix’) relaxation times then shows that the relationship found for superionic glass‐forming systems is inverted in the case of polymer electrolytes. The latter have fractional decoupling indexes which may be interpreted in terms of serial coupling phenomena; i.e. ions must first decouple from their partner ions (in ion pairs), or from their intramolecular solvation states, before they can contribute to conductivity relaxation which is itself coupled to the local polymer matrix relaxation. An extreme case is illustrated using the weak electrolyte, lithium acetate, for which the decoupling index is ∼6 × 10 −5 .