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Structure and transport properties of a plastic crystal ion conductor : Diethyl(methyl)(isobutyl)phosphonium hexafluorophosphate

journal contribution
posted on 01.01.2012, 00:00 authored by Liyu Jin, K Nairn, C Forsyth, A Seeber, D MacFarlane, Patrick HowlettPatrick Howlett, Maria ForsythMaria Forsyth, Jenny PringleJenny Pringle
Understanding the ion transport behavior of organic ionic plastic crystals (OIPCs) is crucial for their potential application as solid electrolytes in various electrochemical devices such as lithium batteries. In the present work, the ion transport mechanism is elucidated by analyzing experimental data (single-crystal XRD, multinuclear solid-state NMR, DSC, ionic conductivity, and SEM) as well as the theoretical simulations (second moment-based solid static NMR line width simulations) for the OIPC diethyl(methyl)(isobutyl)phosphonium hexafluorophosphate ([P1,2,2,4][PF6]). This material displays rich phase behavior and advantageous ionic conductivities, with three solid–solid phase transitions and a highly “plastic” and conductive final solid phase in which the conductivity reaches 10–3 S cm–1. The crystal structure shows unique channel-like packing of the cations, which may allow the anions to diffuse more easily than the cations at lower temperatures. The strongly phase-dependent static NMR line widths of the 1H, 19F, and 31P nuclei in this material have been well simulated by different levels of molecular motions in different phases. Thus, drawing together of the analytical and computational techniques has allowed the construction of a transport mechanism for [P1,2,2,4][PF6]. It is also anticipated that utilization of these techniques will allow a more detailed understanding of the transport mechanisms of other plastic crystal electrolyte materials.

History

Journal

Journal of the American Chemical Society

Volume

134

Issue

23

Pagination

9688 - 9697

Publisher

American Chemical Society

Location

Washington, D.C.

ISSN

0002-7863

eISSN

1520-5126

Language

eng

Publication classification

C1 Refereed article in a scholarly journal