This critical review presents an overview of the various classes of Li⁺ conductors for use as electrolytes in lithium polymer batteries and all-solid state microbatteries. Initially, we recall the main models for ion transport and the structure–transport relationships at the basis of the observed conductivity behaviours. Emphasis is then placed on the physico-chemical and functional parameters relevant for optimal electrolytes preparation, as well as on the techniques of choice for their evaluation. Finally, the state of the art of polymer and ceramic electrolytes is reported, and the most interesting strategies for the future developments are described (121 references).

Polymer fuel cells operating above 100 °C (High Temperature Polymer Electrolyte Membrane Fuel Cells, HT-PEMFCs) have gained large interest for their application to automobiles. The HT-PEMFC devices are typically made of membranes with poly(benzimidazoles), although other polymers, such as sulphonated poly(ether ether ketones) and pyridine-based materials have been reported. In this critical review, we address the state-of-the-art of membrane fabrication and their properties. A large number of papers of uneven quality has appeared in the literature during the last few years, so this review is limited to works that are judged as significant. Emphasis is put on proton transport and the physico‐chemical mechanisms of proton conductivity.

Polybenzimidazole-based membranes are nowadays considered the best alternative to Nafion® for the fabrication of high-temperature polymer fuel cells. The rich chemistry of benzimidazole allows us to widely change the physicochemical properties of the resulting polymers and, consequently, to tune the functional properties of the electrolyte membrane. In this perspective we report the most recent developments in PBI-based membranes, cells and stacks. Emphasis is given to problems such as acid leaching, membrane degradation and stack durability.