Poly(Vinyl Alcohol)/Poly(Acrylic Acid) Gel Polymer Electrolyte Modified with Multi-Walled Carbon Nanotubes and SiO2 Nanospheres to Increase Rechargeability of Zn-Air Batteries.

Zn-air batteries (ZABs) are a promising technology; however, their commercialization is limited by challenges, including those occurring in the electrolyte, and thus, gel polymer electrolytes (GPEs) and hydrogels have emerged as substitutes for traditional aqueous electrolytes. In this work, PVA/PAA membranes were synthesized by the solvent casting method and soaked in 6 M KOH to act as GPEs. The thickness of the membrane was modified (50, 100, and 150 µm), and after determining the best thickness, the membrane was modified with synthesized SiO2 nanospheres and multi-walled carbon nanotubes (CNTs). SEM micrographs revealed that the CNTs displayed lengths of tens of micrometers, having a narrow diameter (95 ± 7 nm). In addition, SEM revealed that the SiO2 nanospheres had homogeneous shapes with sizes of 110 ± 10 nm. Physicochemical experiments revealed that SiO2 incorporation at 5 wt.% increased the water uptake of the PVA/PAA membrane from 465% to 525% and the ionic conductivity to 170 mS cm-1. The further addition of 0.5 wt.% CNTs did not impact the water uptake but it promoted a porous structure, increasing the power density and the stability, showing three-times-higher rechargeability than the ZAB operated with the PVA/PAA GPE.

Properties of the PVA-VAVTD KOH Blend as a Gel Polymer Electrolyte for Zinc Batteries.

Rechargeable zinc-air batteries are promising for energy storage and portable electronic applications because of their good safety, high energy density, material abundance, low cost, and environmental friendliness. A series of alkaline gel polymer electrolytes formed from polyvinyl alcohol (PVA) and different amounts of terpolymer composed of butyl acrylate, vinyl acetate, and vinyl neodecanoate (VAVTD) was synthesized applying a solution casting technique. The thin films were doped with KOH 12M, providing a higher amount of water and free ions inside the electrolyte matrix. The inclusion of VAVTD together with the PVA polymer improved several of the electrical properties of the PVA-based gel polymer electrolytes (GPEs). X-ray diffraction (XRD), thermogravimetric analysis (TGA), and attenuated total reflectance- Fourier-transform infrared spectroscopy (ATR-FTIR) tests, confirming that PVA chains rearrange depending on the VAVTD content and improving the amorphous region. The most conducting electrolyte film was the test specimen 1:4 (PVA-VAVTD) soaked in KOH solution, reaching a conductivity of 0.019 S/cm at room temperature. The temperature dependence of the conductivity agrees with the Arrhenius equation and activation energy of ~0.077 eV resulted, depending on the electrolyte composition. In addition, the cyclic voltammetry study showed a current intensity increase at higher VAVTD content, reaching values of 310 mA. Finally, these gel polymer electrolytes were tested in Zn-air batteries, obtaining capacities of 165 mAh and 195 mAh for PVA-T4 and PVA-T5 sunk in KOH, respectively, at a discharge current of -5 mA.

Development of a Chitosan/PVA/TiO2 Nanocomposite for Application as a Solid Polymeric Electrolyte in Fuel Cells.

The influence of the incorporation of nanoparticles of titanium oxide (TiO2) at a concentration between 1000 and 50,000 ppm on the physicochemical and mechanical properties of a polymer matrix formed from a binary mixture of chitosan (CS) and polyvinyl alcohol (PVA) at a ratio of 80:20 and the possibility of its use as a solid polymeric electrolyte were evaluated. With the mixture of the precursors, a membrane was formed with the solvent evaporation technique (casting). It was found that the incorporation of the nanoparticles affected the moisture absorption of the material; the samples with the highest concentrations displayed predominantly hydrophobic behavior, while the samples with the lowest content displayed absorption values of 90%. Additionally, thermogravimetric analysis (TGA) showed relatively low dehydration in the materials that contained low concentrations of filler; moreover, differential scanning calorimetry (DSC) showed that the nanoparticles did not significantly affect the thermal transitions (Tg and Tm) of the compound. The ionic conductivity of the compound with a relatively low concentration of 1000 ppm TiO2 nanoparticles was determined by complex impedance spectroscopy. The membranes doped with a 4 M KOH solution demonstrated an increase in conductivity of two orders of magnitude, reaching values of 10-6 S·cm-1 at room temperature in previously dried samples, compared to that of the undoped samples, while their activation energy was reduced by 50% with respect to that of the undoped samples. The voltage-current test in a proton exchange membrane fuel cell (PEMFC) indicated an energy efficiency of 17% and an open circuit voltage of 1.0 V for the undoped compound, and these results were comparable to those obtained for the commercial membrane product Nafion® 117 in evaluations performed under conditions of 90% moisture saturation. However, the tests indicated a low current density in the undoped compound.

Influence of Pectin as a green polymer electrolyte on the transport properties of Chitosan-Pectin membranes.

Novel blend membranes have been prepared from Chitosan (CH), Pectin (PEC) and their mixtures. The obtained samples were cross-linked and sulfonated before characterization. The results show that CH/PEC membranes display structural changes on the chemical and physical properties as a function of composition. DSC analysis reveals an endothermic peak due to the scission of the ionic pairs between carboxylic groups and ammonium groups, which produces a strong change on physical properties such as methanol permeability and proton conductivity. The methanol permeability decreases with the amount of Pectin from (4.24±0.04)×10-6cm2/s for pure Chitosan membrane to (1.51±0.03)×10-6cm2/s for blend CH/PEC membranes when the amount of Pectin is 50% (v/v). The proton conductivities of the blend membranes follow a similar behavior. For a pure CH membrane the conductivity is 2.44×10-3S/cm, decreasing with pectin content until the composition 50/50 (v/v), in which the conductivity drops almost one order of magnitude.

Theoretical voltammetric response of electrodes coated by solid polymer electrolyte membranes.

A model for the differential capacitance of metal electrodes coated by solid polymer electrolyte membranes, with acid/base groups attached to the membrane backbone, and in contact with an electrolyte solution is developed. With proper model parameters, the model is able to predict a limit response, given by Mott-Schottky or Gouy-Chapman-Stern theories depending on the dissociation degree and the density of ionizable acid/base groups. The model is also valid for other ionic membranes with proton donor/acceptor molecules as membrane counterions. Results are discussed in light of the electron transfer rate at membrane-coated electrodes for electrochemical reactions that strongly depend on the double layer structure. In this sense, the model provides a tool towards the understanding of the electro-catalytic activity on modified electrodes. It is shown that local maxima and minima in the differential capacitance as a function of the electrode potential may occur as consequence of the dissociation of acid/base molecular species, in absence of specific adsorption of immobile polymer anions on the electrode surface. Although the model extends the conceptual framework for the interpretation of cyclic voltammograms for these systems and the general theory about electrified interfaces, structural features of real systems are more complex and so, presented results only are qualitatively compared with experiments.