Solvent-free low-dimensional polymer electrolytes for lithium-polymer batteries.

The development of solvent-free low-dimensional polymer electrolytes intended for use in solvent-free lithium batteries operating at ambient or sub-ambient temperatures is described. The synthetic routes to the amphiphilic polymers I having 5-alkoxy-3,4-phenylene units connected with oligoethoxy segments via polyester-ether or pure polyether links (abbrev. CmOn, m = 12, 16, 18, n = 1-5) and to the copolymers CmO1-CmOn are described. The structures, thermal properties and SAXS long spacings of their complexes with lithium salts (type A) and with long chain n-alkane or alkyl side chain intercalation (type B) are discussed. However, high ambient conductivities (10(-4)-10(-3) S cm(-1)) are observed in type C systems when a second copolymer based on polytetramethylene oxide segments (II) is incorporated as a microphase between the lamellae of I and serving as an ion bridge or "glue". DC polarization between Li electrodes also gives ambient conductivities >/=ca.10(-3) S cm(-1). In type D systems the I/II interface is stabilized by including a copolymer III, promoting high reproducibility in performance. Copolymers I of CmO1-CmO5 having CmO1 in excess give optimum conductivities with low temperature-dependence. This, together with molecular modeling, suggests uncoupled ion mobilities by hopping between small aggregates in the interlamellar spaces. Copyright 2004 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.