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A study of phase behavior and conductivity of mixtures of the organic ionic plastic crystal N-methyl-N-methyl-pyrrolidinium dicyanamide with sodium dicyanamide
journal contribution
posted on 2015-01-01, 00:00 authored by C Tarekegn, Daniel Gunzelmann, Jitraporn Vongsvivut, Maria ForsythMaria ForsythWe report on the thermal, structural and conductivity properties of the organic ionic plastic crystal (OIPC) N-methyl-N-methyl-pyrrolidinium dicyanamide [C1mpyr][N(CN)2] mixed with the sodium salt Na[N(CN)2]. The DSC thermal traces indicate that an isothermal transition, which may be a eutectic melting, occurs at ~ 89 °C, below which all compositions are entirely in the solid phase. At 20 mol% Na[N(CN)2], this transition is the final melt for this mixture, and a new liquidus peak grows beyond 20 mol% Na[N(CN)2]. The III- > II solid-solid phase transition continues to be evident at ~- 2 °C. The microstructure for all the mixtures indicated a phase separated morphology where precipitates can be clearly observed. Most likely, these precipitates consist of a Na-rich second phase. This was also suggested from the vibrational spectroscopy and the 23Na NMR spectra. The lower concentrations of Na[N(CN)2] present complex 23Na MAS spectra, suggesting more than one sodium ion environment is present in these mixtures consistent with complex phase behavior. Unlike other OIPCs where the ionic conductivity usually increases upon doping or mixing in a second component, the conductivity of these mixtures remains relatively constant and above 10- 4 S cm- 1 at ∼ 80 °C, even in the solid state. Such high conductivities suggest these materials may be promising to be used for all solid-state electrochemical devices.
History
Journal
Solid state ionicsVolume
272Pagination
74 - 83Publisher
ElsevierLocation
Amsterdam, The NetherlandsPublisher DOI
ISSN
0167-2738Language
engPublication classification
C Journal article; C1 Refereed article in a scholarly journalCopyright notice
2015, ElsevierUsage metrics
Keywords
N-methyl-N-methyl-pyrrolidinium dicyanamideOrganic ionic plastic crystalSodiumSolid-state electrolyteSolid-state NMRScience & TechnologyPhysical SciencesChemistry, PhysicalPhysics, Condensed MatterChemistryPhysicsLITHIUM-METAL BATTERIESPROPYLPYRROLIDINIUM TETRAFLUOROBORATEX-RAYSALTSELECTROLYTESDYNAMICSTRANSPORTLIQUIDSSPECTROSCOPYDIFFRACTIONCondensed Matter Physics
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