Human Hemoglobin-Based Zinc-Air Battery in a Neutral Electrolyte.

The use of human hemoglobin (Hb) as a catalytic component of the air electrode in a primary zinc-air battery with a neutral electrolyte has been investigated. Three different electrode modifications, using the drop-casting method, with Hb and Nafion were first tested in a three-electrode cell, obtaining the best oxygen electroreduction (ORR) performance and long-term stability with a Hb plus Nafion (Hb-Nafion)-modified electrode. The latter Hb-Nafion-based air electrode provided a higher specific capacity and discharge time than the opposite order (Nafion-Hb).

Bifunctional P-Containing RuO2 Catalysts Prepared from Surplus Ru Co-Ordination Complexes and Applied to Zn/Air Batteries.

An innovative synthetic route that involves the thermal treatment of selected Ru co-ordination complexes was used to prepare RuO2-based materials with catalytic activity for oxygen reduction (ORR) and oxygen evolution (OER) reactions. Extensive characterization confirmed the presence of Ru metal and RuP3O9 in the materials, with an improved electrocatalytic performance obtained from calcinated [(RuCl2(PPh3)3]. A mechanistic approach for the obtention of such singular blends and for the synergetic contribution of these three species to electrocatalysis is suggested. Catalysts added to carbon-based electrodes were also tested in all-solid and flooded alkaline Zn/air batteries. The former displayed a specific discharge capacity of 10.5 A h g-1 at 250 mA g-1 and a power density of 4.4 kW kg-1 cm-2. Besides, more than 800 discharge/charge cycles were reached in the flooded alkaline Zn/air battery.

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.

A Review of the Use of GPEs in Zinc-Based Batteries. A Step Closer to Wearable Electronic Gadgets and Smart Textiles.

With the flourish of flexible and wearable electronics gadgets, the need for flexible power sources has become essential. The growth of this increasingly diverse range of devices boosted the necessity to develop materials for such flexible power sources such as secondary batteries, fuel cells, supercapacitors, sensors, dye-sensitized solar cells, etc. In that context, comprehensives studies on flexible conversion and energy storage devices have been released for other technologies such Li-ion standing out the importance of the research done lately in GPEs (gel polymer electrolytes) for energy conversion and storage. However, flexible zinc batteries have not received the attention they deserve within the flexible batteries field, which are destined to be one of the high rank players in the wearable devices future market. This review presents an extensive overview of the most notable or prominent gel polymeric materials, including biobased polymers, and zinc chemistries as well as its practical or functional implementation in flexible wearable devices. The ultimate aim is to highlight zinc-based batteries as power sources to fill a segment of the world flexible batteries future market.

A new method based on the Butler-Volmer formalism to evaluate voltammetric cation and anion sensors.

A new method based on the Butler-Volmer formalism is applied to assess the capability of two voltammetric ion sensors based on polypyrrole films: PPy/DBS and PPy/ClO4 modified electrodes were studied as voltammetric cation and anion sensors, respectively. The reversible potential versus electrolyte concentrations semilogarithm plots provided positive calibration slopes for PPy/DBS and negative ones for PPy/ClO4, as was expected from the proposed method and that based on the Nernst equation. The slope expressions deduced from Butler-Volmer include the electron-transfer coefficient, which allows slope values different from the ideal Nernstian value to be explained. Both polymeric films exhibited a degree of ion-selectivity when they were immersed in mixed-analyte solutions. Selectivity coefficients for the two proposed voltammetric cation and anion sensors were obtained by several experimental methods, including the separated solution method (SSM) and matched potential method (MPM). The K values acquired by the different methods were very close for both polymeric sensors.

In situ FTIR spectroscopy study of the break-in phenomenon observed for PPy/PVS films in acetonitrile.

The in situ Fourier transform infrared (in situ FTIR) technique was used for the first time to investigate the break-in phenomenon observed for polypyrrole/poly(vinyl sulfonate) (PPy/PVS) films in acetonitrile containing 0.1 M LiClO(4). Consecutive potential scans provided a continuous increase of the infrared band intensities, simultaneous to an increase observed in the charge involved in the voltammetric peaks, suggesting a rise in the number of the polymeric chains participating in the infrared signal at the same time as the electroactive participants increase in the redox process. Moreover, in situ FTIR spectra evidence that the new infrared-activated chains in each voltammetric cycle adopt the same polymeric structure achieved by the chains activated in the initial cycles. However, if we achieve a cathodic potential limit of -2.1 V (vs Ag/AgCl), a restructuring of the polymeric morphology is observed. In situ FTIR spectra obtained for PPy/ClO(4) films under the same conditions pointed to a steady-state behavior from the very early voltammetric scans. Moreover, the intensities of FTIR bands obtained for PPy/ClO(4) films in the early voltammetric cycles are much higher than those obtained for PPy/PVS films after several potential scans. Only when high cathodic and high anodic potential limits were used for the consecutive cycles did the FTIR band intensities from PPy/PVS become similar to those obtained from PPy/ClO(4), indicating that in both films a similar number of polymeric chains were infrared active. Polarization at a high anodic potential (+1.3 V vs Ag/AgCl) produced overoxidation of the polymer appearing characteristic 1725 cm(-1) band assigned to the formation of carbonyl groups. Furthermore, the approximately 1540 cm(-1) band shifted to higher wavenumbers, indicating that overoxidation reduced the length of conjugated chains in the polypyrrole.