Highly Conducting Bombyx mori Silk Fibroin-Based Electrolytes Incorporating Glycerol, Dimethyl Sulfoxide and [Bmim]PF6

abstract

Green, transparent and flexible electrolyte films composed of a Bombyx mori silk fibroin (SF) host biopolymer doped with glycerol (G), dimethyl sulfoxide (DMSO, D) and 1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim]PF6) ionic liquid (IL), were synthesized. The materials were represented by the notation SF@GD@ILx (x = 15, 20 and 30 is the mass ratio of SF/[Bmim]PF6 in %). SF@, SF@G, SF@D and SF@GD samples were also prepared. DMSO was found to play a dual-role, acting as solvent of [Bmim]PF6, and enhancing ionic conductivity. DMSO, alone or combined with [Bmim]PF6, led to the increase of the mean roughness and induced the formation of more ordered Silk II conformations (beta-sheets). No structural modifications were detected in the SF@GD@ILx samples upon increasing the temperature up to 100 degrees C. The highest ionic conductivity was exhibited by the IL-rich sample SF@GD@IL30 (1.07 and 4.61 mS cm(-1), at 22 and 100 degrees C, respectively). In the [Bmim]PF6-doped electrolytes free and coordinated PF6- ions coexist. The weight losses occurring below 200 degrees C involved essentially the release of adsorbed water and DMSO. The suitable mechanical properties, high ionic conductivity and good electrochemical stability suggest that these electrolytes are attractive candidates for application in electrochemical devices. (C) 2020 The Author(s). Published on behalf of The Electrochemical Society by IOP Publishing Limited.

keywords

IONIC-LIQUID; MECHANICAL-PROPERTIES; SCAFFOLDS; FILMS; HEXAFLUOROPHOSPHATE; FABRICATION; CHALLENGES; BATTERIES; MEMBRANES; FIBERS

subject category

Electrochemistry; Materials Science

authors

Fernandes, TCD; Rodrigues, HMR; Paz, FAA; Sousa, JFM; Valente, AJM; Silva, MM; Bermudez, VD; Pereira, RFP

our authors

acknowledgements

Veronica de Zea Bermudez would like to express her gratitude to Professor Michel Armand who, during her PhD thesis at Grenoble (1989-1992), was an endless source of ideas that made her work productive and stimulating. His qualities, as an inspiring and extraordinary scientist, equal his kindness, generosity and great heart. This work was supported by National funds by Foundation for Science and Technology (FCT) in the framework of the Strategic Funding UID/QUI/00686/2018, UID/QUI/00686/2019, UID/QUI/50006/2019 and UID/QUI/00313/2020. The authors thank FEDER funds through the COMPETE 2020 Program and National Funds through FCT under the projects PEst-OE/QUI/UI0616/2014, LUMECD (POCI-01-0145-FEDER-016884 and PTDC/CTMNAN/0956/2014), UniRCell (POCI-01-0145-FEDER-016422 and SAICTPAC/0032/2015), PORPLANTSURF (POCI-01-0145FEDER-029785 and PTDC/CTM-REF/29785/2017), and NORTE01-0145-FEDER-030858. R.F.P.P thanks FCT-UM for the researcher contract in the scope of Decreto-Lei 57/2016 and 57/2017. H.M.R. Goncalves was funded by PTDC/BTM-MAT/30858/2017.

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