Ionic conductivity of polymer electrolytes containing branched poly (ethylene imine) (BPEI) and lithium bis(trifluoromethyl sulfonyl)imide (LiTESI) was measured between temperatures of 20 and 70 degrees C and molar ratios of 20:1 and 400:1. The electrolytes were characterized by impedance spectroscopy, differential scanning calorimetry, and viscosity measurements. At room temperature, the maximum conductivity was 2 x 10(-6) S/cm at a molar ratio of 50:1. The molar conductivity of the electrolytes displayed first a minimum and then a maximum upon increasing salt concentration. A proportionality of molar conductivity to segmental mobility was seen from glass transition temperature and viscosity measurements. Analysis of the Walden product and isoviscosity conductivity showed that the percentage of ions bound in ion pairs increased at low concentrations below 0.1 mol/kg. The average dipole moment decreased with salt concentration. The temperature dependence of the ionic conductivity showed an Arrhenius behavior. (C) 2011 Elsevier Ltd. All rights reserved.