Prussian blue analogues are considered as promising candidates for aqueous sodium-ion batteries providing a decently high energy density for stationary energy storage. However, suppose the operation of such materials under high-power conditions could be facilitated. In that case, their application might involve fast-response power grid stabilization and enable short-distance urban mobility due to fast re-charging. In this work, sodium nickel hexacyanoferrate thin-film electrodes are synthesized via a facile electrochemical deposition approach to form a model system for a robust investigation. Their fast-charging capability is systematically elaborated with regard to the electroactive material thickness in comparison to a ″traditional″ composite-type electrode. It is found that quasi-equilibrium kinetics allow extremely fast (dis)charging within a few seconds for sub-micron film thicknesses. Specifically, for a thickness below ≈ 500 nm, 90% of the capacity can be retained at a rate of 60C (1 min for full (dis)charge). A transition toward mass transport control is observed when further increasing the rate, with thicker films being dominated by this mode earlier than thinner films. This can be entirely attributed to the limiting effects of solid-state diffusion of Na+ within the electrode material. By presenting a PBA model cell yielding 25 Wh kg–1 at up to 10 kW kg–1, this work highlights a possible pathway toward the guided design of hybrid battery–supercapacitor systems. Furthermore, open challenges associated with thin-film electrodes are discussed, such as the role of parasitic side reactions, as well as increasing the mass loading.

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Electrochemical Impedance Spectroscopy (EIS) has been widely applied for Li-ion battery research because EIS can reflect the physical characteristics. The full impedance spectrum sweep generally takes several minutes. Thus, it is impossible to implement a full spectrum sweep for real-time investigations. In this paper, machine learning approach is proposed to address the issue. The proposed approach is based on multi-sine signal sweep technique, where the impedances at corresponding frequencies are derived with a fast Fourier transform. The full impedance spectrum is obtained via machine learning approach. The results are compared with three alternative techniques namely, the piecewise cubic Hermite interpolation polynomial, modified Akima piecewise cubic Hermite interpolation, and Spline. The results demonstrate that the proposed machine learning approach has the best performance.

Niobium belongs to the group of refractory metals, and shows advanced properties such as a high melting point and a good hardness, due to the strong interatomic bonds [1,2]. Furthermore, niobium exhibits excellent chemical and corrosion resistance [3]. This makes niobium coatings very attractive for a broad spectrum of applications [4]. Due to the low standard potential, it is not possible to electrodeposit niobium from aqueous solutions. Ionic liquids (ILs) are a good alternative, and first studies have demonstrated the general feasibility of Nb metal deposition from NbF5 containing ILs [5-7]. However, layers deposited from standard ionic liquids like 1-butyl-1-methylpyrrolidinium bistrifluoromethylsulfonyl imide (BMP TFSI) often still are not dense, show cracks, have residual ionic liquids incorporated, and contain Nb subhalides [5]. The use of different precursors like NbCl5 and other ionic liquids, particularly those based on a triflate anion, has been reported [8-10]. In our own research, we recently studied in detail the electrochemical reduction of NbCl5 in TFSI-based ionic liquids [11]. In this work, the electrochemical behavior of NbF5 in different ionic liquids was studied with the electrochemical quartz crystal microbalance technique (EQCM). A network analyzer was used to measure the admittance between the two Au electrodes (one serving as working electrode) of 10 MHz quartz resonators in parallel to the electrochemical measurements. This permitted to extract both changes in resonance frequency and damping of the quartz. The latter is particularly important in ionic liquids, as local changes in the electrolyte composition due to a reduction process are often associated with damping changes. Experiments were carried out at different temperatures, using pulsed electrodeposition and pulsed ultrasound techniques. The application of ultrasound can significantly enhance mass transport and thereby prevent precursor depletion and fluoride enrichment at the surface. On the downside, there is a risk of accelerated electrolyte degradation [11, 12]. Figure 1a shows an example for a successful deposition from a 0.25 M NbF5 solution in an alkylammonium IL electrolyte. A reasonably well adhering layer was obtained even at room temperature that however still contained some fluoride ions at the surface, and was very rough. According to the XPS measurements in Figure 1b and c, an average composition of NbF0.6 was obtained at the surface. Figure 1. a) Photograph of layer deposited from 0.25 M NbF5 b) XPS spectrum (F1s) c) XPS spectrum (Nb 3p5/2,3/2) References [1] S. Zein El Abedin, H.K. Farag, E.M. Moustafa, U. Welz-Biermann, F. Endres. Phys. Chem. Chem. Phys., 7, 2333 (2005). [2] N. Borisenko, A. Ispas, E. Zschippang, Q. Liu, S. Zein El Abedin, A. Bund, F. Endres, Electrochim. Acta, 54, 1519 (2009). [3] V.-H. Pham, S.-H. Lee, Y. Li, H.-E. Kim, K.-H. Shin, Y.-H. Koh, Thin Solid Films, 536, 269 (2013). [4] F. Cardarelli, Int. J. of Refractory Metals & Hard Materials, 14, 3655 (1996). [5] P. Giridhar, S. Zein El Abedin, A. Bund, A. Ispas, F. Endres, Electrochim. Acta, 129, 312 (2014). [6] S. Krischok, A. Ispas, A. Zühlsdorff, A. Ulbrich, A. Bund, F. Endres, ECS Trans., 50(11), 229 (2012). [7] A. Vacca, M. Mascia, L. Mais, S. Rizzardini, F. Delogu, S. Palmas, Electrocatalysis, 5, 16 (2014). [8] E. Freydina, and J. G. Abbott, ECS Trans., 75 (15), 639 (2016). [9] O. B. Babushkina, E. O. Lomako, and W. Freyland, Electrochim. Acta, 62, 234 (2012). [10] Endrikat, N. Borisenko, A. Ispas, R. Peipmann, F. Endres, A. Bund; under revision. [11] L. Seidl, L. Asen, G. Yesilbas, P. Fischer, F. Kühn, and O. Schneider, ECS Trans., 86 (14), 3 (2018). [12] J. D. Oxley, T. Prozorov, and K. S. Suslick, J. Am. Chem. Soc., 125 (37), 11138 (2003). Figure 1

With the in-depth application of quartz crystal microbalance (QCM) sensors in the fields of science and engineering, there is an urgent need for QCM sensors with high mass sensitivity. The mass sensitivity of a QCM is closely related to its resonance frequency, and the high resonance frequency leads to improve its mass sensitivity. However, the resonance frequency of a QCM resonator cannot be increased all the time due to the fragility of quartz wafer and the limits of energy trapping effect. Few studies are associated with mass sensitivity of a QCM resonator under overtone modes. Herein, we propose to make a QCM resonator work in its n-th overtone (n = 3, 5, 7, 9 in this study) mode to increase its resonance frequency during operating. Thereby, the purpose of improving QCM mass sensitivity is achieved, and the mass sensitivity of a QCM working in the n-th overtone mode can be called as n-th overtone mass sensitivity. Then, the n-th overtone mass sensitivity of a QCM sensor is measured by an electrodeposition method. The experimental results show that the n-th overtone mass sensitivity of a QCM is a bit more than n times that of the fundamental mass sensitivity, and it is consistent with the theoretical calculation results. The application of overtone mass sensitivity will greatly improve the sensitivity of QCM sensors, which is very attractive for the research fields that require QCM sensors with high sensitivity.

This contribution discusses the application of ultrasound in ionic liquids (ILs) and its effect on refractory metal deposition as well as the particular electrochemistry of NbCl5 in TFSI based ILs. A systematic study was carried out studying electrochemical reactions and electrolyte decomposition in the presence of ultrasound. Extended application of ultrasound induced partial IL decomposition and formation of solid precipitates. Electrochemical reactions in ILs were enhanced by ultrasound application. Especially the application of short ultrasound pulses at elevated temperatures increased electrochemical reaction rates. The reduction of NbCl5 from BMP and OMP TFSI ILs is characterized by five separate distinct reduction and corresponding oxidation steps. This system was studied in depth using the electrochemical quartz crystal microbalance technique, revealing strong changes in the electrolyte properties close to the interface.

Sensing sensitivity is one of the crucial parameters for quartz crystal microbalance (QCM) sensors. Herein, we study the overtone mass sensitivity of a QCM sensor with an asymmetric N-M type electrode configuration. In order to overcome the deficiency that the sensitivity of the QCM sensor with an asymmetric electrode cannot be calculated by Sauerbrey's equation, we design the electrochemical electrodeposition experiments to measure it. The measurement results of overtone mass sensitivities of three 3.