Systematics of salt precipitation in complexes of polyethylene oxide and alkali metal iodides

Conductivity measurements in PEO 30 MI polymer electrolytes with M = Li, Na, K, Rb, or Cs over the temperature range from about 65 to 200 ° C show an increasing tendency for salt precipitation with increasing cation size. The salt precipitation in these complexes upon heating is revealed by the decrease of the dc conductivity starting at a critical temperature T c . Whereas Lil and Nal complexes do not show precipitation effects, T c monotonically decreases from about 140 to 65 °C when changing the salt component from K1 via RbI to Csl. For the PEO-RbI system, precipitation is further investigated by nuclear magnetic resonance (NMR) and tracer diffusion experiments. NMR analysis unambiguously demonstrates the onset of RbI salt precipitation and the increase of the precipitate fraction with increasing temperature. In diffusion experiments on PEO 30 RbI with the radiotracers 86 Rb and 125 I, the precipitation effect is manifested by anomalous features in the penetration profiles, however, without noticeable changes in their depth range. Combining the resulting tracer diffusion coefficients with the dc conductivity data enables us to assess crucial parameters characterizing ionic transport in PEO 30 RbI.