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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 2003-01-01, 00:00 authored by A Seeber, Maria ForsythMaria Forsyth, C Forsyth, S Forsyth, G Annat, D MacFarlaneN,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 physicsVolume
5Issue
12Pagination
2692 - 2698Publisher
Royal Society of ChemistryLocation
Cambridge, EnglandPublisher DOI
ISSN
1463-9076eISSN
1463-9084Language
engPublication classification
C1.1 Refereed article in a scholarly journalCopyright notice
2003, Owner SocietiesUsage metrics
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No categories selectedKeywords
Science & TechnologyPhysical SciencesChemistry, PhysicalPhysics, Atomic, Molecular & ChemicalChemistryPhysicsX-RAY-DIFFRACTIONPROTON MAGNETIC-RESONANCEDIFFERENTIAL THERMAL-ANALYSISELECTRICAL-CONDUCTIVITYMOLECULAR MOTIONSROTATOR PHASESOLID-PHASESSELF-DIFFUSIONTRIMETHYLETHYLAMMONIUM IODIDEION CONDUCTION
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