Abstract

Abstract An overview is given on polymer electrolytes based on organo-functionalized polyphosphazenes and polysiloxanes. Chemical and electrochemical properties are discussed with respect to the synthesis, the choice of side groups and the goal of obtaining membranes and thin films that combine high ionic conductivity and mechanical stability. Electrochemical stability, concentration polarization and the role of transference numbers are discussed with respect to possible applications in lithium batteries. It is shown that the ionic conductivities of salt-in-polymer membranes without additives and plasticizers are limited to maximum conductivities around 10-4S/cm. Nevertheless, a straightforward strategy based on additives can increase the conductivities to at least 10-3S/cm and maybe further. In this context, the future role of polymers for safe, alternative electrolytes in lithium batteries will benefit from concepts based on polymeric gels, composites and hybrid materials. Presently developed polymer electrolytes with oligoether sidechains are electrochemically stable in the potential range 0–4.5V (vs. Li/Li+ reference).

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