The electrochemical behavior of magnetite (Fe3O4) aggregates with submicrometric size is investigated. Specifically, cyclic voltammetry tests were performed in both acidic (pH ∼ 4.5) and alkaline (pH ∼ 12.8) solutions, exploiting a conventional three-electrode cell. In the first case, the working electrode was made of a glassy carbon substrate loaded with magnetite nanoaggregates, forming a continuous film. In a second configuration, magnetite nanoaggregates were dispersed in solution, kept under stirring, as a fluidized electrode. The latter approach showed an increase in the electrochemical response of the particles, otherwise limited by the reduced active area as in the former case. Electrochemical-atomic force microscopy (EC-AFM) investigation was carried out in an acidic environment, showing the topography evolution of nanoaggregates during the electrochemical characterization. X-ray diffraction (XRD) analysis was carried out to evaluate the microstructural variation in the Fe3O4 electrodes after cathodic polarization tests in an alkaline environment.
Sodium-ion batteries (SIBs) represent a cost-effective and sustainable alternative to lithium-ion battery (LIBs).1 One of the main issues of SIB technology is the higher ionic radius of sodium, compared to lithium, which limits the cyclability due to unfavourable intercalation of Na+ ions into carbon-based anodes.2 Anode-free batteries represents a promising approach to improve the cyclability, changing the working principle at the anode from intercalation of Na+ ions to electrodeposition metallic sodium.3 Moreover, thanks to the anode-free configuration the energy density of the overall device can be drastically increased. To efficiently control the electrodeposition of the metallic layer of sodium, the current collector must be carefully designed. Copper nanofoams were produced by dynamic hydrogen-bubble template (DHBT) as high-surface area template for the sodium electrodeposition, as an innovative alternative to the traditionally flat electrodes. The electrodeposition of sodiophilic materials, i.e. tin and antimony, onto the nanofoam, was also investigated to control the nucleation of the metallic layer at the anode.4 Sn and Sb baths were optimized to guarantee an homogeneous distribution of the sodiophilic metal on the nanofoam. The morphology and the composition of the nanofoams was characterized and electrochemical characterization was performed in half-cell configuration, showing coulombic efficiency higher than 99% and good cyclability for 100 cycles, for both Sn and Sb compositions compared to the bare Cu. This demonstrates the feasibility of the usage of sodiophilic nanofoams as current collectors in anode-free sodium batteries. Vaalma, C., Buchholz, D., Weil, M. & Passerini, S. A cost and resource analysis of sodium-ion batteries. Nat. Rev. Mater. 2018 34 3, 1–11 (2018). Irisarri, E., Ponrouch, A. & Palacin, M. R. Review—Hard Carbon Negative Electrode Materials for Sodium-Ion Batteries. J. Electrochem. Soc. 162, A2476–A2482 (2015). Cohn, A. P. et al. Rethinking sodium-ion anodes as nucleation layers for anode-free batteries. J. Mater. Chem. A 6, 23875–23884 (2018). Seh, Z. W., Sun, J., Sun, Y. & Cui, Y. A highly reversible room-temperature sodium metal anode. ACS Cent. Sci. 1, 449–455 (2015).
Nowadays, electrochemical energy storage systems have gaining interest because they constitute an essential element in the development of sustainable energy technologies [1,2]. Among them, rechargeable flow batteries (RFBs) are one of the most promising technology for the integration in grid-connected electricity, especially if combined with unpredictable and intermittent renewable energy sources, due to their high efficiency, power/energy independent sizing and room temperature operation [3]. At the moment, among all RFBs systems, the most investigated and advanced technology is the vanadium based RFB, characterized by an energy efficiency equal to 80% and energy density ranging 15-45 Wh/l [4]. However, currently the main bulk of research is focused on finding an economically convenient and technically competitive flow battery chemistry, able to ensure long lifetime and high energy efficiency [5,6]. In this study, a zinc-iodine RFB with low cost and high energy density will be presented. In particular, inorganic electrolytes based on high soluble salts have been developed to increase the charge density of the device. Moreover, a deep study on the effects of organic additive for the proper zinc developed electrolyte, aiming to reduce the dendrites growth and to increase the current efficiency, have been analyzed. In order to investigate the effect of these chemical compounds, the developed solutions have been characterized by means of cyclic voltammetries while the obtained zinc metallic coatings have been morphological characterized using scanning electron microscopy. The combination of high energy efficiency of the Zn-I RFB, in the order of 70% at 20 mA cm-2, with its very high energy density ranging from 25 to 60 Wh/l, depending on the formulation of the electrolytes, its ability to withstand a large number of charge/discharge cycles and the low cost, makes this battery system suitable for large energy storage applications. References P. Alotto, M. Guarnieri, and F. Moro. Renewable and Sustainable Energy Reviews 29 (2014): 325-335. A. Z. Weber, M.M. Mench,, J.P. Meyers, P.N. Ross, J.T. Gostick and Q. Liu. Journal of Applied Electrochemistry (2011), 41(10), 1137. G. Kear, A.A Shah, and F.C. Walsh. International journal of energy research, (2012), 36(11), 1105-1120. C. Ding, H. Zhang, X. Li, T. Liu, and F. Xing. The Journal of Physical Chemistry Letters, (2013), 4(8), 1281-1294. C- Xie, Y. Duan, W. Xu, H. Zhang, and X Li. Angewandte Chemie International Edition, (2017) 56(47), 14953-14957. S. Selverston, R. F. Savinell, and J. S. Wainright. Journal of The Electrochemical Society 164.6 (2017): A1069-A1075.
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