Study of Proton Transport in Diethylmethylammonium Poly[4-styrenesulfonyl(trifluoromethylsulfonyl)imide]-Based Composite Membranes with Triflic Acid and Diethylmethylamine-Rich Compositions

Azhar Hussain Shah, Usman Ali Rana, Haijin Zhu*, Jiaye Li, R. Vijayaraghavan, Douglas R. Macfarlane, Maria Forsyth, Humaira M. Siddiqi*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

2 Scopus citations

Abstract

The study highlights the effect of acid- and base-rich conditions on the proton dynamics of diethylmethylammonium poly[4-styrenesulfonyl(trifluoromethylsulfonyl)imide, [DEMA][PSTFSI], a polymerized protic ionic liquid designed as a polymer electrolyte for nonhumidified polymer electrolyte membrane fuel cells. Different proportions of triflic acid (HTf) and diethylmethylamine (DEMA) were added to the pristine polymer. The thermal analysis of the mixtures revealed that the addition of the base increases the glassy/amorphous nature of the polymer; however, HTf plasticizes the polymer and lowers the Tg value, so that it falls outside of the differential scanning calorimetry-studied temperature range. 50 mol % doping of the HTf contents increases the conductivity upto 0.952 mS cm-1, and 50 mol % DEMA mixture has a conductivity of 0.169 mS cm-1 at 100 °C. Vogel-Tamman-Fulcher fitting of the ionic conductivities of the doped systems suggested that the ionic conductivities are completely decoupled from segmental motion of the polymer. A combination of Fourier transform infrared and static NMR studies demonstrated that HTf-added polymer composites show conduction via Grotthuss and vehicular mechanisms, while DEMA-added polymer composites show predominantly a Grotthuss mechanism by developing the aggregates of proton and added base.

Original languageEnglish
Pages (from-to)11005-11016
Number of pages12
JournalJournal of Physical Chemistry B
Volume125
Issue number39
DOIs
StatePublished - 7 Oct 2021
Externally publishedYes

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