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Efficiency of the grid energy storage technology based on iron-chloride material cycle
Uroš Luin, doctoral dissertation

Abstract: Future high-capacity energy storage technologies are crucial for a highly renewable energy mix, and their mass deployment must rely on cheap and abundant materials, such as iron chloride. The iron chloride electrochemical cycle (ICEC), suitable for long-term grid energy storage using a redox potential change of Fe2+/Fe, involves the electrolysis of a highly concentrated aqueous FeCl2 solution yielding solid iron deposits. For the high overall energy efficiency of the cycle, it is crucial maximizing the energy efficiency of the electrolysis process. The thesis presents a study of the influence of electrolysis parameters on energy efficiency, performed in an industrial-type electrolyzer system. We studied the conductivity of the FeCl2 solution as a function of concentration and temperature and correlated it with the electrolysis energy efficiency as a function of current density. The contribution of the resistance polarization increases with the current density, causing a decrease in overall energy efficiency. The highest energy efficiency of 89 ±3 % was achieved using 2.5 mol dm-3 FeCl2 solution at 70 °C and a current density of 0.1 kA m-2. In terms of the energy input per Fe mass, this means 1.88 Wh g-1. The limiting energy input per mass of the Fe-deposit, calculated by extrapolating experimental results toward Eocell potential, was found to be 1.76 Wh g-1. For optimal long-duration electrolysis efficiency and performance, the optimal catholyte concentration range is 1-2 mol dm-3 FeCl2. We performed in situ X-ray absorption spectroscopy experimental studies to validate theoretical conclusions from literature related to the population and structure of Fe-species in the FeCl2 (aq) solution at different concentrations (1 - 4 mol dm-3) and temperatures (25 - 80 °C). This revealed that at low temperature and low FeCl2 concentration, the octahedral first coordination sphere around Fe is occupied by one Cl ion at a distance of 2.33 (±0.02) Å and five H2O at a distance of 2.095 (±0.005) Å. The structure of the ionic complex gradually changes with an increase in temperature and/or concentration. The apical H2O is substituted by a Cl ion to yield a neutral Fe[Cl2(H2O)4]0. The transition from the charged Fe[Cl(H2O)5]+ to the neutral Fe[Cl2(H2O)4]0 causes a significant drop in the solution conductivity, which well correlates with the existing state-of-the-art conductivity models. An additional steric impediment of the electrolytic cell is caused by the predominant neutral species present in the catholyte solution at high concentration. This correlates with poor electrolysis performance at a very high catholyte concentration (4 mol dm-3 FeCl2), especially at high current densities (> 1 kA m-2). The neutral Fe[Cl2(H2O)4]0 complex negatively affects the anion exchange membrane ion (Cl-) transfer and lowers the concentration of electroactive species (Fe[Cl(H2O)5]+) at the cathode surface. The kinetics of hydrogen evolution from the reaction between Fe powder and HCl acid was studied under the first-order reaction condition. The activation energy was determined to be 55.3 kJ mol-1.
Keywords: ICEC, Power-to-Solid, energy storage, hydrogen, ferrous chloride, electrolysis, Fe deposition, efficiency, XAS, structure and population, ionic species, ion association, conductivity
Published in RUNG: 18.04.2023; Views: 561; Downloads: 20  (1 vote)
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Plasma-enhanced atomic layer deposition of amorphous Ga2O3 for solar-blind photodetection
Ze-Yu Fan, Min-Ji Yang, Bo-Yu Fan, Andraž Mavrič, Nadiia Pastukhova, Matjaž Valant, Bo-Lin Li, Kuang Feng, Dong-Liang Liu, Guang-Wei Deng, Qiang Zhou, Yan-Bo Li, 2022, original scientific article

Abstract: Wide-bandgap gallium oxide (Ga2O3) is one of the most promising semiconductor materials for solar-blind (200 nm–280 nm) photodetection. In its amorphous form, a-Ga2O3 maintains its intrinsic optoelectronic properties while can be prepared at a low growth temperature, thus is compatible with Si integrated circuits (ICs) technology. Herein, the a-Ga2O3 film is directly deposited on pre-fabricated Au interdigital electrodes by plasma enhanced atomic layer deposition (PE-ALD) at a growth temperature of 250 °C. The stoichiometric a-Ga2O3 thin film with a low defect density is achieved owing to the mild PE-ALD condition. As a result, the fabricated Au/a-Ga2O3/Au photodetector shows a fast time response, high responsivity, and excellent wavelength selectivity for solar-blind photodetection. Furthermore, an ultra-thin MgO layer is deposited by PE-ALD to passivate the Au/a-Ga2O3/Au interface, resulting in the responsivity of 788 A/W (under 254 nm at 10 V), a 250-nm-to-400-nm rejection ratio of 9.2×103, and the rise time and the decay time of 32 ms and 6 ms, respectively. These results demonstrate that the a-Ga2O3 film grown by PE-ALD is a promising candidate for high-performance solar-blind photodetection and potentially can be integrated with Si ICs for commercial production.
Keywords: Amorphous gallium oxide, Passivation layer, Plasma enhanced atomic layer deposition, Responsivity, Solar-blind photodetector
Published in RUNG: 25.10.2022; Views: 629; Downloads: 0
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Evolution of fractal dimension in pulsed laser deposited MoO3 film with ablation time and annealing temperature
Swapna Mohanachandran Nair Sindhu, 2021, original scientific article

Abstract: The multifractal analysis is a potential method for assessing thin flm surface morphology and its changes due to diferent deposition conditions and post-deposition treatments. In this work, the multifractal analysis is carried out to understand the surface morphology—root mean square (RMS) surface roughness—of nanostructured MoO3 flms prepared by pulsed laser deposition technique by varying the ablation time and post-deposition annealing. The XRD analysis shows the evolution of crystalline nature with annealing temperature. The XRD pattern of all the annealed flms shows the characteristic peak of the orthorhombic MoO3 phase. The FESEM and AFM analysis reveals the morphological modifcation with ablation time and annealing temperature. The multifractal analysis of the AFM images shows that the box—counting, information and correlation dimension varies with the annealing temperature. The study also reveals the inverse relation between the fractal dimension and the RMS surface roughness due to the annealing induced particle size variation and reorientation. The fractal dimension’s evolution in the pulsed laser deposited MoO3 flm with ablation time and annealing temperature is also investigated. Thus, the study reveals the potential of multifractal analysis in the thin flm surface characterizatio
Keywords: Multifractal analysis · Pulsed laser deposition · Molybdenum oxide · Atomic force microscopy · Fractal dimension
Published in RUNG: 04.07.2022; Views: 728; Downloads: 0
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Electrolysis energy efficiency of highly concentrated FeCl[sub]2 solutions for power-to-solid energy storage technology
Uroš Luin, Matjaž Valant, 2022, original scientific article

Abstract: An electrochemical cycle for the grid energy storage in the redox potential of Fe involves the electrolysis of a highly concentrated aqueous FeCl2 solution yielding solid iron deposits. For the high overall energy efficiency of the cycle, it is crucial to maximize the energy efficiency of the electrolysis process. Here we present a study of the influence of electrolysis parameters on the energy efficiency of such electrolysis, performed in an industrial-type electrolyzer. We studied the conductivity of the FeCl2 solution as a function of concentration and temperature and correlated it with the electrolysis energy efficiency. The deviation from the correlation indicated an important contribution from the conductivity of the ion-exchange membrane. Another important studied parameter was the applied current density. We quantitatively showed how the contribution of the resistance polarization increases with the current density, causing a decrease in overall energy efficiency. The highest energy efficiency of 89 ± 3% was achieved using 2.5 mol L−1 FeCl2 solution at 70 °C and a current density of 0.1 kA m−2. In terms of the energy input per Fe mass, this means 1.88 Wh g−1. The limiting energy input per mass of the Fe deposit was found to be 1.76 Wh g−1.
Keywords: electrolysis, ferrous chloride, iron deposition, energy efficiency
Published in RUNG: 16.02.2022; Views: 1193; Downloads: 71  (1 vote)
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Atomic layer deposition for the photoelectrochemical applications
Nadiia Pastukhova, Andraž Mavrič, Yanbo Li, 2021, review article

Abstract: Substantial progress has been made in the photoelectrochemical (PEC) field to understand the photoelectrode behavior, semiconductor‐electrolyte interface, and photocorrosion, enabling new photoelectrode architectures with higher photocurrent, reduced photovoltage losses, and longer lifetime. Nevertheless, for practical PEC applications additional efforts are still needed to optimize all components of the photoelectrodes, including the light absorbing semiconductors, the layers for charge extraction, charge transfer, corrosion protection, and catalysis. In this regard, atomic layer deposition (ALD) offers new opportunities due to the monolayer‐by‐monolayer deposition approach, allowing preparation of conformal films with precisely controlled thickness and composition. As the ALD instruments are becoming widely accessible, this review aims to make an overview of the applications for photoelectrodes fabrication. The deposition of semiconductors onto flat and nano‐textured substrates, the deposition of ultrathin interlayers to ease charge transport by energy band alignment and surface states passivation, the deposition of corrosion protection layers, and finally, the possibilities for high catalyst dispersion is presented.
Keywords: atomic layer deposition, charge recombination, charge transfer, photocorrosion, photoelectrochemical water splitting
Published in RUNG: 25.02.2021; Views: 1800; Downloads: 136
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Synthesis of a Cu/ZnO Nanocomposite by Electroless Plating for the Catalytic Conversion of CO2 to Methanol
Maja Pori, Iztok Arčon, Damjan Lašič Jurković, Marjan Marinšek, Goran Dražić, Blaž Likozar, Zorica Crnjak Orel, 2019, original scientific article

Abstract: The process of methanol synthesis based on the hydrogenation of CO2 was investigated over binary Cu/ZnO catalyst materials, prepared by applying a novel electroless plating fabrication method. The activity of the produced catalytic samples was determined at temperature range between 200 and 300 °C and the feedstock conversion data were supplemented with a detailed microstructure analysis using high-resolution transmission electron microscopy (HRTEM), X-ray powder diffraction (XRD) and Cu and Zn K-edge, X-ray absorption near-edge structure (XANES) measurements and extended X-ray absorption fine-structure (EXAFS) measurements. It was confirmed that the disorder in the Cu crystallites created unique geometrical situations, which acted as the additional reactive centres for the adsorption of the reactant molecule species. Copper and zinc structural synergy (spill-over) was also demonstrated as being crucial for the carbon dioxide’s activation. EXAFS and XANES results provide strong evidence for surface alloying between copper and zinc and thus the present results demonstrate new approach applicable for explaining metal–support interactions.
Keywords: EXAFS, CuZn alloy, Spillover mechanism, CO2 valorization, Electroless deposition method, Heterogeneous catalysis
Published in RUNG: 12.04.2019; Views: 3103; Downloads: 0
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CVD Growth of Molybdenum Diselenide Surface Structures with Tailored Morphology
M. Naeem Sial, Usman Muhammad, Binjie Zheng, Yanan Yu, Andraž Mavrič, Fangzhu Qing, Matjaž Valant, Zhiming M. Wang, 2018, original scientific article

Abstract: Controllable atmospheric pressure CVD has been optimized to grow transition metal dichalcogenide MoSe2 with tunable morphology at 750 °C on a silicon substrate with a native oxide layer of 250 nm. Utilizing tetrapotassium perylene-3,4,9,10-tetracarboxylate (PTAS) as a seed promoter and varying the vertical distance between the substrate and the precursor MoO3, different morphologies of MoSe2 were achieved, including 2D triangles, hexagons, 3D pyramids and vertically aligned MoSe2 sheets. We find that the shape of MoSe2 is highly dependent upon the distance h between the substrate and the precursor. The change in the morphology is attributed to the confinement of vapor (MoO3 and Se) precursors and their concentrations due to the change in h. These results are helpful in improving our understanding about the factors which influence the morphology (shape evolution) and also the continuous growth of MoSe2 films.
Keywords: Transition metal dichalcogenides, 2D materials, Seed promotor, Chemical vapor deposition, Molybdenum diselenide
Published in RUNG: 20.08.2018; Views: 3285; Downloads: 11
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Novel two-step vapor-phase synthesis of UV – Vis light active Fe2O3/WO3 nanocomposites for phenol degradation
Davide Barreca, Giorgio Carraro, Alberto Gasparotto, Chiara Maccato, Cinzia Sada, Elza Bontempi, Mariangela Brisotto, Olena Pliekhova, Urška Lavrenčič Štangar, 2016, original scientific article

Abstract: Supported Fe2O3/WO3 nanocomposites were fabricated by an original vapor phase approach, involving the chemical vapor deposition (CVD) of Fe2O3 on Ti sheets and the subsequent radio frequency (RF)-sputtering of WO3. Particular attention was dedicated to the control of the W/Fe ratio, in order to tailor the composition of the resulting materials. The target systems were analyzed by the joint use of complementary techniques, that is, X-ray diffraction (XRD), field emission-scanning electron microscopy (FE-SEM), atomic force microscopy (AFM), energy dispersive X-ray spectroscopy (EDXS), X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS), and optical absorption spectroscopy. The results showed the uniform decoration of α-Fe2O3 (hematite) globular particles by tiny WO3 aggregates, whose content could be controlled by modulations of the sole sputtering time. The photocatalytic degradation of phenol in the liquid phase was selected as a test reaction for a preliminary investigation of the system behavior in wastewater treatment applications. The system activity under both UVand Vis light illumination may open doors for further material optimization in view of real-world end-uses.
Keywords: Fe2O3, WO3, Nanocomposites, Chemical vapor deposition, Sputtering, Photocatalysis
Published in RUNG: 03.08.2016; Views: 4483; Downloads: 0
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