RESUMO
The structure of a polymer electrolyte, P(EO)7.5LiN(SO 2CF (3))(2), has been determined by neutron diffraction with isotropic substitution. The Li ions are bonded on average to five ether oxygens belonging to pairs of PEO coils. These are arranged with a considerable degree of extended-range order providing pathways for the Li ion conduction. The lack of ion pairing in this system below 4.8 A is reminiscent of that observed in the remarkable structure of P(EO)6LiAsF (6) and implies that anions and cations are free to migrate independently.
RESUMO
The relation between mechanical and electrical relaxation in polymer/lithium-salt complexes is a fascinating and still unresolved problem in condensed-matter physics, yet has an important bearing on the viability of such materials for use as electrolytes in lithium batteries. At room temperature, these materials are biphasic: they consist of both fluid amorphous regions and salt-enriched crystalline regions. Ionic conduction is known to occur predominantly in the amorphous fluid regions. Although the conduction mechanisms are not yet fully understood, it is widely accepted that lithium ions, coordinated with groups of ether oxygen atoms on single or perhaps double polymer chains, move through re-coordination with other oxygen-bearing groups. The formation and disruption of these coordination bonds must be accompanied by strong relaxation of the local chain structure. Here we probe the relaxation on a nanosecond timescale using quasielastic neutron scattering, and we show that at least two processes are involved: a slow process with a translational character and one or two fast processes with a rotational character. Whereas the former reflects the slowing-down of the translational relaxation commonly observed in polyethylene oxide and other polymer melts, the latter appears to be unique to the polymer electrolytes and has not (to our knowledge) been observed before. A clear picture emerges of the lithium cations forming crosslinks between chain segments and thereby profoundly altering the dynamics of the polymer network.
