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Conductivity, NMR and crystallographic study of N,N,N,N-tetramethylammonium dicyanamide plastic crystal phases : an archetypal ambient temperature plastic electrolyte material

journal contribution
posted on 01.01.2003, 00:00 authored by A Seeber, Maria ForsythMaria Forsyth, C Forsyth, S Forsyth, G Annat, D MacFarlane
N,N,N,N-Tetramethylammonium dicyanamide (Me4NDCA) has been examined via differential scanning calorimetry (DSC), thermogravimetric analysis, conductivity, single crystal X-ray diffraction and 1H nuclear magnetic resonance (NMR) analyses, and was found to be highly conductive in the solid state (σ =10−3 S cm−2 at 420 K) and to also exhibit unusual plastic crystal behaviour. To investigate the correlation between such behaviour and the occurrence of molecular rotations in the crystal, 1H NMR second moment measurements are compared with calculated values predicted from the crystal structure. While DSC analysis indicates a number of solid–solid transitions at ambient temperatures, subsequent 1H NMR analysis of the Me4N+ cation shows that a variety of rotational motions become active at low (<240 K) temperatures, and that such transitions in rotational states occur over a range of temperatures rather than in a sharp transition. Conductivity analysis reveals that between 320 K and 420 K the conductivity increases by more than six orders of magnitude in the solid state, in line with the transition of the Me4N+ cation to a diffusive state, and that other phase transitions observed in this temperature range have no marked effect on the conductivity. Conduction in this solid state is therefore envisaged to involve a vacancy-diffusion model, involving Me4N+ cation vacancies.

History

Journal

Physical chemistry chemical physics

Volume

5

Issue

12

Pagination

2692 - 2698

Publisher

Royal Society of Chemistry

Location

Cambridge, England

ISSN

1463-9076

eISSN

1463-9084

Language

eng

Publication classification

C1.1 Refereed article in a scholarly journal

Copyright notice

2003, Owner Societies