Chemistry Research Centre of the University of Minho

Funder

Organizational Unit

Publications

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

Publication . Fernandes, Tânia C. D.; Gonçalves, Helena M R; Paz, Filipe A. A.; Sousa, Joana F. M.; Valente, Artur J. M.; Silva, Maria M.; Zea Bermudez, Verónica de; Pereira, Rui F. P.

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 (β-sheets). No structural modifications were detected in the SF@GD@ILx samples upon increasing the temperature up to 100 °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 °C, respectively). In the [Bmim]PF6-doped electrolytes "free" and coordinated PF6− ions coexist. The weight losses occurring below 200 °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.

2020Journal article

Open access

Electrochromic Device Composed of a Di-Urethanesil Electrolyte Incorporating Lithium Triflate and 1-Butyl-3-Methylimidazolium Chloride

Publication . Gonçalves, Maria Cristina; Pereira, Rui F. P.; Alves, Raquel; Nunes, Sílvia C.; Fernandes, Mariana; Gonçalves, Helena M R; Pereira, Sónia; Silva, M. Manuela; Fortunato, Elvira; Rego, Rosa; Zea Bermudez, Verónica de

A di-urethane cross-linked poly(oxyethylene)/silica hybrid matrix [di-urethanesil, d-Ut(600)], synthesized by the sol-gel process, was doped with lithium triflate (LiCF3SO3) and the 1-butyl-3-methylimidazolium chloride ([Bmim]Cl) ionic liquid. The as-produced xerogel film is amorphous, transparent, flexible, homogeneous, hydrophilic, and has low nanoscale surface roughness. It exhibits an ionic conductivity of 3.64 × 10–6 and 5.00 × 10–4 S cm–1 at 21 and 100°C, respectively. This material was successfully tested as electrolyte in an electrochromic device (ECD) with the glass/ITO/a-WO3/d-Ut(600)10LiCF3SO3[Bmim]Cl/c-NiO/ITO/glass configuration, where a-WO3 and c-NiO stand for amorphous tungsten oxide and crystalline nickel oxide, respectively. The device demonstrated attractive electro-optical performance: fast response times (1–2 s for coloring and 50 s for bleaching), good optical memory [loss of transmittance (T) of only 41% after 3 months, at 555 nm], four mode modulation [bright mode (+3.0 V, T = 77% at 555 nm), semi-bright mode (−1.0 V, T = 60% at 555 nm), dark mode (−1.5 V, T = 38 % at 555 nm), and very dark mode (−2.0 V, T = 11% and −2.5 V, T = 7% at 555 nm)], excellent cycling stability denoting improvement with time, and high coloration efficiency [CEin = −6727 cm2 C–1 (32th cycle) and CEout = +2794 cm2 C–1 (480th cycle), at 555 nm].

2020Journal article

Open access