Structure and Transport Properties of a Plastic Crystal Ion Conductor: Diethyl(methyl)(isobutyl)phosphonium Hexafluorophosphate

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• 作者：Liyu Jin ; Kate M. Nairn ; Craig M. Forsyth ; Aaron J. Seeber ; Douglas R. MacFarlane ; Patrick C. Howlett ; Maria Forsyth ; Jennifer M. Pringle
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：June 13, 2012
• 年：2012
• 卷：134
• 期：23
• 页码：9688-9697
• 全文大小：591K
• 年卷期：v.134,no.23(June 13, 2012)
• ISSN：1520-5126

文摘

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 ([P_1,2,2,4][PF₆]). This material displays rich phase behavior and advantageous ionic conductivities, with three solid鈥搒olid phase transitions and a highly 鈥減lastic鈥?and conductive final solid phase in which the conductivity reaches 10^鈥? S cm^鈥?. 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 [P_1,2,2,4][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.