1. Beyond surface area : enhanced pseudocapacitive properties of cobalt layered double hydroxide through structural modificationsAnja Siher, Ksenija Maver, Uroš Luin, Albin Pintar, Iztok Arčon, Andraž Mavrič, 2025, original scientific article Abstract: Cobalt hydroxide and other first-row transition metal hydroxides have gained significant attention as pseudocapacitor materials due to their rapid and reversible redox processes. Their layered structures facilitate interactions between electrolyte anions and cobalt cation sites within the bulk of the material, enabling higher charge density and extending redox activity beyond the particle surface. By controlled precipitation under hydrothermal conditions, the structure and morphology of cobalt hydroxides can be optimized to enhance electrochemical performance. Challenging conventional assumptions, surface area alone is not the primary factor driving increased pseudocapacitive performance. The hexagonal hydrotalcite-like structure, characterized by lower skeletal density and larger basal plane spacing, outperforms the monoclinic cobalt carbonate hydroxide structure, achieving an order of magnitude higher capacitance. In situ X-ray absorption spectroscopy provides critical insights into the pseudocapacitive behavior, revealing enhanced accessibility of Co2+ sites for electrochemical oxidation. While monoclinic cobalt carbonate hydroxide exhibits minimal changes in the Co2+ oxidation state, indicative of surface-limited redox activity, the hydrotalcite-like cobalt hydroxides show substantial shifts in the Co K-edge position, highlighting oxidation of Co2+ sites throughout the bulk. Keywords: pseudocapacitors, layered-double hydroxides, cobalt hydroxide, redox processes, in situ x-ray absorption spectroscopy Published in RUNG: 14.03.2025; Views: 621; Downloads: 7
Full text (1,48 MB) This document has many files! More... |
2. Iodine K- and L-edge X-ray absorption spectra of HI : the effect of molecular orbitals and core subshellsRobert Hauko, Jana Padežnik Gomilšek, Alojz Kodre, Iztok Arčon, Uroš Luin, 2024, original scientific article Abstract: Analysis of the recently measured absorption spectra of molecular HI at K and L edges of iodine, in parallel with
previously measured spectra of noble gas Xe and the K edge spectrum of atomic I, is presented. A strong
dependence of some valence multielectron photoexcitation features on the orbital momentum of the core vacancy
is found, attributed to the change of the symmetry of the HI molecule: the shake-up coexcitation of a
valence electron to a free molecular orbital is much stronger at L3 than L1 edge. The effect of angular momentum
of the core hole on the shake processes of deeper multielectron photoexcitations is found negligible. Both HI and
Xe exhibit a much weaker one-electron transition [1s]6p than monatomic I. At the K edge, the strength of
coexcitations of 4d, 4p and 3d subshells in atomic I is close to the HI and Xe. The same is found for HI and Xe at
the L edges, due to a weak contribution of the additional free molecular orbital in HI. Keywords: X-ray absorption spectroscopy, K edge spectrum of atomic I, multielectron photoexcitations (MEPE), core vacancy angular momentum Published in RUNG: 09.01.2025; Views: 766; Downloads: 6
Link to file This document has many files! More... |
3. Environmental priorities in the circular economy : examples from iron-based technologiesAndreea Oarga-Mulec, Uroš Luin, Keith R. Skene, Matjaž Valant, 2024, published scientific conference contribution Abstract: The circular economy (CE) framework is crucial for promoting resource efficiency and minimizing waste, but it cannot achieve its sustainability goals alone. To achieve a truly sustainable future, broader social, environmental and economic aspects need to be taken into account. Rather than separating biological and technological cycles, as the CE principles are depicted in the Ellen MacArthur Foundation’s butterfly diagram (EMF, 2017), we propose an integrated approach that prioritises environmental aspects and includes a conceptual framework, socio-economic changes and implementation processes. It is crucial to re-evaluate the environmental aspects and strengthen their importance within the CE framework. Within this concept we present the case of iron, the most widely used metal, widely available compared to others and has been an essential part of societal development for more than 5,000 years. With its abundance, safety and electrochemical properties, iron is an ideal material for low-carbon energy technologies. We discuss how advanced iron-based technologies have a high potential to be successfully integrated into the CE, we evaluate different electrochemical energy storage systems and present advances in thermochemical Fe-Cl cycles for hydrogen production. An innovative thermal system for hydrogen production based on the thermochemical Fe-Cl cycle was evaluated in a life cycle assessment (LCA) study and shows the importance of choosing sustainable energy sources to minimise environmental impact. Sustainable production methods for iron are also analysed to demonstrate their potential to reduce the carbon footprint of the iron and steel industry. Finally, efforts should focus on minimising environmental impact and optimising resource recovery. Keywords: circular economy, resource efficiency, sustainability, iron, hydrogen Published in RUNG: 25.11.2024; Views: 1015; Downloads: 0 This document has many files! More... |
4. Back to the future with emerging iron technologiesAndreea Oarga-Mulec, Uroš Luin, Matjaž Valant, 2024, review article Abstract: Here is a comprehensive overview of iron's potential in low-carbon energy technologies, exploring applications like metal fuel combustion, iron-based batteries, and energy-carrier cycles, as well as sustainable approaches for production and recycling with a focus on reducing environmental impact. Iron, with its abundance, safety, and electrochemical characteristics, is a promising material to contribute to a decarbonized future. This paper discusses the advancements and challenges in iron-based energy storage technologies and sustainable iron production methods. Various innovative approaches are explored as energy storage solutions based on iron, like advancements in thermochemical Fe–Cl cycles highlight the potential of iron chloride electrochemical cycles for long-term high-capacity energy storage technology. Additionally, the utilization of iron as a circular fuel in industrial processes demonstrates its potential in large-scale thermal energy generation. Sustainable iron production methods, such as electrolysis of iron chloride or oxide and deep eutectic solvent extraction, are investigated to reduce the carbon footprint in the iron and steel industry. These findings also show the importance of policy and technology improvements that are vital for the widespread use and recycling of iron-based tech, stressing the need for collaboration toward a sustainable future. Keywords: iron's potential, low-carbon energy technologies Published in RUNG: 02.07.2024; Views: 2211; Downloads: 8
Full text (457,19 KB) This document has many files! More... |
5. Chemistry of the iron-chlorine thermochemical cycle for hydrogen production utilizing industrial waste heatMatjaž Valant, Uroš Luin, 2024, original scientific article Abstract: This research presents an inventive thermochemical cycle that utilizes a reaction between iron and HCl acid for hydrogen production. The reaction occurs spontaneously at room temperature, yielding hydrogen and a FeCl2 solution as a by-product. Exploring the thermal decomposition of the FeCl2 by-product revealed that, at conditions suitable for utilization of low-temperature industrial waste heat (250 °C), chlorine gas formation can be circumvented. Instead, the resulting by-product is HCl, which is readily soluble in water, facilitating direct reuse in subsequent cycles. The utilization of low-temperature industrial heat not only optimizes resource utilization and reduces operational costs but also aligns with environmentally sustainable production processes. From the kinetic studies the activation energy was calculated to be 45 kJ/mol and kinetics curves were constructed. They showed significant kinetics at room temperature and above but rapid decrease towards lower temperatures. This is important to consider during real-scale technology optimization. The theoretical overall energy efficiency of the cycle, with 100% and 70% heat recuperation, was calculated at 68.8% and 44.8%, respectively. In practical implementation, considering the efficiency of DRI iron reduction technology and free waste heat utilization, the cycle achieved a 41.7% efficiency. Beyond its energy storage capabilities, the Iron-chlorine cycle addresses safety concerns associated with large-scale hydrogen storage, eliminating self-discharge, reducing land usage, and employing cost-effective storage materials. This technology not only facilitates seasonal energy storage but also establishes solid-state energy reserves, making it suitable for balancing grid demands during winter months using excess renewable energy accumulated in the summer. Keywords: chemical cycles, hydrogen production, thermal decomposition, reaction kinetics, iron, chlorine Published in RUNG: 12.01.2024; Views: 2998; Downloads: 45
Full text (3,80 MB) This document has many files! More... |
6. Efficiency of the grid energy storage technology based on iron-chloride material cycleUroš 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: 3269; Downloads: 50 (1 vote)
Full text (4,34 MB) |
7. Correlation between FeCl2 electrolyte conductivity and electrolysis efficiencyUroš Luin, Matjaž Valant, Iztok Arčon, 2022, published scientific conference contribution abstract Abstract: The electrolysis efficiency is an important aspect of the Power-to-Solid energy storage technology (EST) based
on the iron chloride electrochemical cycle [1]. This cycle employs an aqueous FeCl2 catholyte solution for the
electro-reduction of iron. The metal iron deposits on the cathode. The energy is stored as a difference in the
redox potential of iron species. Hydrogen, as an energy carrier, is released on demand over a fully controlled
hydrogen evolution reaction between metallic Fe0 and HCl (aq) [1]. Due to these characteristics, the cycle is
suitable for long-term high-capacity and high-power energy storage. In a previous work [2] we revealed that
the electrolyte conductivity linearly increases with temperature. Contrary, the correlation between the
electrolyte concentration and efficiency is not so straightforward. Unexpectedly small efficiency variations were
found between 1 and 2.5 mol dm-3 FeCl2 (aq) followed by an abrupt efficiency drop at higher concentrations.
To explain the behavior of the observed trends and elucidate the role of FeCl2 (aq) complex ionic species we
performed in situ X-ray absorption studies. We made a dedicated experimental setup, consisting of a tubular
oven and PMMA liquid absorption cell, and performed the measurements at the DESY synchrotron P65
beamline. The XAS investigation covered XANES and EXAFS analyses of FeCl2 (aq) at different
concentrations (1 - 4 molL-1) and temperatures (25 - 80 °C). We found 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 water molecules at a distance of 2.095 (±0.005) Å [3]. The structure of the ionic complex
gradually changes with an increase in temperature and/or concentration. The apical water molecule is
substituted by a chlorine ion to yield a neutral Fe[Cl2(H2O)4]0. The transition from the single 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 conductivity models [3].
[1] M. Valant, “Procedure for electric energy storage in solid matter. United States Patent and
Trademark Office. Patent No. US20200308715,” Patent No. US20200308715, 2021.
[2] U. Luin and M. Valant, “Electrolysis energy efficiency of highly concentrated FeCl2 solutions
for power-to-solid energy storage technology,” J. Solid State Electrochem., vol. 26, no. 4, pp.
929–938, Apr. 2022, doi: 10.1007/S10008-022-05132-Y.
[3] U. Luin, I. Arčon, and M. Valant, “Structure and Population of Complex Ionic Species in
FeCl2 Aqueous Solution by X-ray Absorption Spectroscopy,” Molecules, vol. 27, no. 3, 2022,
doi: 10.3390/molecules27030642. Keywords: Iron chloride electrochemical cycle, Power-to-Solid energy storage, XANES, EXAFS, electrical
conductivity, electrolyte complex ionic species structure and population Published in RUNG: 26.09.2022; Views: 3436; Downloads: 0 (1 vote) This document has many files! More... |
8. |
9. Electrolysis energy efficiency of highly concentrated FeCl[sub]2 solutions for power-to-solid energy storage technologyUroš 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: 3688; Downloads: 81 (1 vote)
Full text (1,99 MB) This document has many files! More... |
10. Structure and population of complex ionic species in FeCl[sub]2 aqueous solution by X-ray absorption spectroscopyUroš Luin, Iztok Arčon, Matjaž Valant, 2022, original scientific article Abstract: Technologies for mass production require cheap and abundant materials such as ferrous chloride (FeCl2). The literature survey shows the lack of experimental studies to validate theoretical conclusions related to the population of ionic Fe-species in the aqueous FeCl2 solution. Here, we present an in situ X-ray absorption study of the structure of the ionic species in the FeCl2 aqueous solution at different concentrations (1–4 molL−1) and temperatures (25–80 ◦C). We found 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 water molecules 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 water molecule is substituted by a chlorine ion to yield a neutral Fe[Cl2(H2O)4]0. The observed substitutional mechanism is facilitated by the presence of the intramolecular hydrogen bonds as well as entropic reasons. The transition from the single 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 conductivity models. Keywords: structure, population, ionic species, aqueous ferrous chloride, in situ X-ray absorption spectroscopy Published in RUNG: 24.01.2022; Views: 3310; Downloads: 44 (1 vote)
Link to full text This document has many files! More... |