Poly(ionic liquid)s-based nanocomposite polyelectrolytes with tunable ionic conductivity prepared via SI-ATRP

Abstract

In this study, a novel kind of organic-inorganic core-shell SiO 2 -poly(p-vinylbenzyl) trimethylammonium tetrafluoroborate (SiO 2 -P[VBTMA][BF 4 ]) nanoparticle was well designed and successfully synthesized via surface-initiated atom transfer radical polymerization (SI-ATRP). Fourier transform infrared spectroscopy (FT-IR), 1 H nuclear magnetic resonance ( 1 H NMR), X-ray photoelectron spectroscopy (XPS), dynamic light scattering (DLS) and scanning electron microscopy (SEM) were used to confirm the formation of the core-shell nanoparticles and the surface modification. In order to overcome the challenge of the characterization of the number average molecular weight of poly(ionic liquid)s, "sacrificial initiator" method was used here employing a trimethylsilyl (TMS)-labeled initiator as the NMR marker for integration. In addition, good thermal stability of the new hybrid polyelectrolyte was proved by thermogravimetric analysis. The electrochemical impedance measurements revealed that the room temperature conductivity reached 10 À4 S cm À1 , which is much higher than that of the pure poly(ionic liquid)s and varies with the amount of the grafted polymer and the test temperature. The X-ray diffraction (XRD) tests further investigated the crystal structure of the nanocomposite and pure P [VBTMA][BF 4 ]. The temperature dependence of ionic conductivity conforms to Arrhenius behavior for both of the nanocomposites and the pure polymer. The results indicated that the SI-ATRP approach provided a simple and versatile route to tune the ionic conductivity of the hybrid nanoparticles by changing the chain length of the grafted polymer, which can be potentially used in a variety of electrochemical devices.

Architecture, Assembly, and Emerging Applications of Branched Functional Polyelectrolytes and Poly(ionic liquid)s

“…Polymeric brushes based on ionic liquid monomers are also reported but outside the scope of this review. 36,140,143 To …”

A review of polymer electrolytes: fundamental, approaches and applications

“…In order to prevent electrolyte leakage, it is important to convert the RTIL-based electrolyte solution into a quasi-solid or solid form. In general, there are three techniques used to prepare highly conductive RTILbased GPE: doping the PEs with ionic liquids, in situ polymerizing the monomers in RTILs and polymerizing the polymerizable ILs that contains the functional groups [165,175,176]. However, the RTIL-based GPEs have some drawbacks which limit the applications, such as poor mechanical and dimensional stabilities, that fortunately can be overcome by the incorporation of fillers [44].…”

Harnessing Poly(ionic liquid)s for Sensing Applications

“…To fabricate the sensor, the composite thin film was placed between two electrodes and their resistance was measured by electrochemical impedance spectroscopy (Figure C). At an optimum weight ratio of PIL and nanoparticle (60–80 wt% La 2 O 2 CO 3 ), the interfacial interaction between PIL and the nanoparticles was maximized and resulted in a significant drop in resistance through the formation of charge transfer highways . Additionally, the interaction between the negatively charged particles and the cationic PIL resulted in increased anion mobility and thus a further decrease in resistance (Figure D).…”