The melting behaviour and transport properties of straight chain alkanes mono- and difunctionalized with phosphonic acid groups have been investigated as a function of their length. The increase of melting temperature and decrease of proton conductivity with increasing chain length is suggested to be the consequence of an increasing ordering of the alkane segments which constrains the free aggregation of the phosphonic acid groups. However, the proton mobility is reduced to a greater extent than the proton diffusion coefficient indicating an increasing cooperativity of proton transport with increasing length of the alkane segment. The results clearly indicate that the "spacer concept", which had been proven successful in the optimization of the proton conductivity of heterocycle based systems, fails in the case of phosphonic acid functionalized polymers. Instead, a very high concentration of phosphonic acid functional groups forming "bulky" hydrogen bonded aggregates is suggested to be essential for obtaining very high proton conductivity. Aggregation is also suggested to reduce condensation reactions generally observed in phosphonic acid containing systems. On the basis of this understanding, the proton conductivities of poly(vinyl phosphonic acid) and poly(meta-phenylene phosphonic acid) are discussed. Though both polymers exhibit a substantial concentration of phosphonic acid groups, aggregation seems to be constrained to such an extent that intrinsic proton conductivity is limited to values below sigma = 10(-3) S cm(-1) at T = 150 degrees C. The results suggest that different immobilization concepts have to be developed in order to minimize the conductivity reduction compared to the very high intrinsic proton conductivity of neat phosphonic acid under quasi dry conditions. In the presence of high water activities, however, (as usually present in PEM fuel cells) the very high ion exchange capacities (IEC) possible for phosphonic acid functionalized ionomers (IEC >10 meq g(-1)) may allow for high proton conductivities in the intermediate temperature range (T approximately 120 -160 degrees C).
Among so-called “next generation” battery technologies, lithium metal batteries (LMBs) enabled by solid-state electrolytes are considered key to achieve rechargeable batteries with higher energy density and safety than current lithium ion batteries (LIBs). This article briefly evaluates various aspects of polymer electrolytes from history, macromolecular architecture, material classification, and electrode optimization, with special emphasis on solid polymer electrolytes (SPEs) and single ion conducting polymeric electrolytes. Representative interfaces and interphases as well as corresponding engineering strategies adopted for the anticipated goals are briefly summarized, including various approaches adopted to mitigate the shortcomings at the interfaces. Significant weight should be given for research and development of SPEs, as they could be an enabler for solid-state LMBs with attractive performance and made by comparatively easy electrode and cell processing techniques.
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