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Ionic transport through a composite structure of N-ethyl-N-methylpyrrolidinium tetrafluoroborate organic ionic plastic crystals reinforced with polymer nanofibres

Iranipour, N., Gunzelmann, D. J., Seeber, A., Vongsvivut, J., Doherty, C., Ponzio, F., O'Dell, L. A., Hollenkamp, A. F., Forsyth, M. and Howlett, P. C. 2015, Ionic transport through a composite structure of N-ethyl-N-methylpyrrolidinium tetrafluoroborate organic ionic plastic crystals reinforced with polymer nanofibres, Journal of materials chemistry a, vol. 3, no. 11, pp. 6038-6052, doi: 10.1039/c4ta07155g.

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Title Ionic transport through a composite structure of N-ethyl-N-methylpyrrolidinium tetrafluoroborate organic ionic plastic crystals reinforced with polymer nanofibres
Author(s) Iranipour, N.
Gunzelmann, D. J.
Seeber, A.
Vongsvivut, J.
Doherty, C.
Ponzio, F.
O'Dell, L. A.ORCID iD for O'Dell, L. A. orcid.org/0000-0002-7760-5417
Hollenkamp, A. F.
Forsyth, M.ORCID iD for Forsyth, M. orcid.org/0000-0002-4273-8105
Howlett, P. C.ORCID iD for Howlett, P. C. orcid.org/0000-0002-2151-2932
Journal name Journal of materials chemistry a
Volume number 3
Issue number 11
Start page 6038
End page 6052
Total pages 15
Publisher Royal Society of Chemistry
Place of publication Cambridge, Eng.
Publication date 2015-03-21
ISSN 2050-7488
2050-7496
Keyword(s) Science & Technology
Physical Sciences
Technology
Chemistry, Physical
Energy & Fuels
Materials Science, Multidisciplinary
Chemistry
Materials Science
PHASE-BEHAVIOR
PROPYLPYRROLIDINIUM TETRAFLUOROBORATE
BIS(TRIFLUOROMETHANESULFONYL) AMIDE
TEMPERATURE-DEPENDENCE
ENHANCED CONDUCTIVITY
ELECTROLYTES
LIQUID
DYNAMICS
SPECTRA
SALTS
Summary The incorporation of polyvinylidene difluoride (PVDF) electrospun nanofibres within N-ethyl-N-methylpyrrolidinium tetrafluoroborate, [C2mpyr][BF4] was investigated with a view to fabricating self-standing membranes for various electrochemical device applications, in particular lithium metal batteries. Significant improvement in mechanical properties and ionic conduction was demonstrated in a previous study, which also demonstrated the remarkably high performance of the lithium-doped composite material in a device. We now seek a fundamental understanding of the role of fibres within the matrix of the plastic crystal, which is essential for optimizing device performance through fine-tuning of the composite material properties. The focus of the current study is therefore a thorough investigation of the phase behaviour and conduction behaviour of the pure and the lithium-doped (as LiBF4) plastic crystal, with and without incorporation of polymer nanofibres. Analysis of the structure of the plastic crystal, including the effects of lithium ions and the incorporation of PVDF fibres, was conducted by means of synchrotron XRD. Ion dynamics were evaluated using VT solid-state NMR spectroscopy. ATR-FTIR spectroscopy was employed to gain insights into the molecular interactions of doped lithium ions and/or the PVDF nanofibres in the matrix of the [C2mpyr][BF4] composites. Preliminary measurements using PALS were conducted to probe structural defects within the pure materials. It was found that ion transport within the plastic crystal was significantly altered by doping with lithium ions due to the precipitation of a second phase in the structure. The incorporation of the fibres activated more mobile sites in the systems, but restricted ion mobility with different trends being observed for each ion species in each crystalline phase. In the presence of the fibres a strong interaction observed between the Li ion and the pyrrolidinium ring disappeared and formation of the second phase was prevented. As a result, an increased number of mobile lithium ions are released into the solid solution structure of the matrix, simultaneously removing the blocking effect of the second phase. Thus, ion conduction was remarkably improved within the Li-doped composite compared to the neat Li-doped plastic crystal.
Language eng
DOI 10.1039/c4ta07155g
Field of Research 100708 Nanomaterials
Socio Economic Objective 970103 Expanding Knowledge in the Chemical Sciences
HERDC Research category C1 Refereed article in a scholarly journal
ERA Research output type C Journal article
Copyright notice ©2015, Royal Society of Chemistry
Persistent URL http://hdl.handle.net/10536/DRO/DU:30075396

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