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Akolkar, Rohan (ORCID:0000000298655704)

Publications and source records attributed to Akolkar, Rohan (ORCID:0000000298655704).

Editors’ Choice—Molten Salt Electrolysis in Chloride Melts for Energy-Efficient Iron Metal Production

This study explores chloride molten salt electrolysis (CMSE) as a promising route for energy-efficient iron metal (Fe) production. Moderate temperature (500 °C) LiCl-KCl molten salts offer excellent thermodynamic stability, high ionic conductivity and diffusivity, and high solubility for FeCl 3 , thereby enabling efficient Fe metal extraction at high electrowinning rates. Here, we demonstrate the two essential steps for converting taconite ore into Fe metal. First, Fe 2 O 3 from taconite pellets was selectively leached in HCl yielding a high-purity FeCl 3 aqueous solution, while the gangue components settled at the bottom. Then, anhydrous FeCl 3 was electrolyzed in a LiCl-KCl eutectic molten salt at 500 °C at high current density (1 A cm −2 ) and at high Coulombic efficiency (>85%). Analysis of the electrowon Fe deposits revealed dendritic structures with purity of >99 wt%, which could be further improved to nearly 100 wt% through arc re-melting. CMSE offers low specific energy consumption (3.7 kWhr kg −1 ), competitive with H 2 -DRI and other electrolytic approaches being pursued globally. Our findings underscore the potential of CMSE as an energy-efficient route for electrosynthesis of Fe metal.

36 MATERIALS SCIENCE↗

A Modified Sand’s Time Incorporating Li-Ion Transport Across the SEI: Basis for Understanding Li Dendrite Formation and Li-Metal Battery Electrolyte Selection

Abstract Understanding the initiation of lithium dendrites remains elusive, largely due to the intricate role of the solid electrolyte interphase (SEI) which forms on the Li surface during electrodeposition. Many studies have utilized the classical Sand’s equation to estimate the onset time when lithium dendrites begin to form. The Sand’s equation provides the time when the cation (Li+) concentration at the electrode-electrolyte interface approaches zero under diffusion-limited conditions in galvanostatic Li electrodeposition. However, recent experimental studies have revealed that the observed lithium dendrite onset time deviates considerably from the Sand’s time. Here, we show that this deviation from classical theory is likely due to the transport of Li+ ions through the SEI - a transport limitation that is much more dominant in controlling dendrite formation. We develop a ‘modified’ Sand's equation, incorporating the SEI layer and the diffusional transport across it to predict Li dendrite onset times. To validate this approach, we conducted Li electrodeposition experiments at various current densities using two distinct organic electrolytes. Analysis of the results demonstrates that the modified Sand's equation provides a more accurate prediction of dendrite onset times, highlighting the importance of incorporating SEI into transport models of Li plating in next-generation rechargeable Li-metal batteries.

Ma, Yuanman (ORCID:0000000200444811)↗

Potential–Dependent BDAC Adsorption on Zinc Enabling Selective Suppression of Zinc Corrosion for Energy Storage Applications

Utility-scale zinc (Zn) batteries are a promising solution to address the problem of intermittency of renewable energy sources; however, Zn-metal anodes in these batteries suffer from capacity loss due to spontaneous corrosion of the Zn especially when high-surface area anode configurations are employed. Additionally, Zn dendrites are known to form during battery charging limiting the cycle-life of these batteries. Electrolyte additives have been explored that prevent aforementioned issues, but these too come at a cost, i.e., surface-blocking additives polarize the electrode surface leading to loss in the voltaic and energy efficiencies of the battery. In this contribution, a novel electrolyte additive, benzyldimethylhexadecylammonium chloride (BDAC), is investigated for its ability to suppresses corrosion of Zn in an acidic (pH = 3) electrolyte. An attribute of BDAC distinct from previously studied additives is that it selectively suppresses electrochemical activity when the Zn electrode is at its corrosion potential; however, during high-rate Zn deposition (charging) or stripping (discharging), BDAC is essentially deactivated and thus it does not appreciably polarize the electrode surface, thus minimizing voltaic efficiency losses. This selective corrosion suppression behavior is explored using slow-scan voltammetry, which reveals hysteresis implying a potential- or current-dependent BDAC adsorption mechanism in which BDAC reaches higher surface coverages when the partial currents at the Zn surface are low (e.g., at or near the corrosion potential), but BDAC coverage is reduced considerably when the Zn deposition or stripping rates are increased. Numerical simulations of the BDAC diffusion-adsorption process corroborate this mechanism. Ramifications of our approach to the selective suppression of Zn dendrites are discussed.

25 ENERGY STORAGE↗

Perspective—Is Sustainable Electrowinning of Neodymium Metal Achievable?

Rare–earth metals such as neodymium are central to numerous technologically important applications such as electrified transportation, renewable energy harvesting, and magnetic data storage. Presently, neodymium metal is produced via electrolysis of Nd 2 O 3 –containing NdF 3 –LiF molten salts at high temperatures. However, this conventional electrolytic route has several drawbacks including emissions of greenhouse gases such as CO 2 and perfluorocarbons, which are harmful to the environment. In this perspective, an alternate concept based on electrolysis of NdCl 3 –containing chloride–based molten salts is explored and its potential advantages are discussed. Notably, NdCl 3 can be obtained via direct non–carbothermic chlorination of Nd 2 O 3 , supported by thermodynamic calculations and experimental evidence from literature. The chloride–based molten salt electrolysis route also offers the possibility of incorporating a non–consumable or dimensionally stable anode leading to reduced electrical energy consumption, stable cell operation and ease of process scalability.

36 MATERIALS SCIENCE↗

The Future of Nuclear Energy: Electrochemical Reprocessing of Fuel Takes Center Stage

Nuclear power plants use energy-dense fuel and provide dependable baseload energy without generating greenhouse gas emissions. Despite these advantages, the long-term management of used nuclear fuel (UNF) remains a key challenge due to its lifetime (hundreds of thousands of years) and radiotoxicity. The components of UNF that contribute the most to this challenge are the actinide elements. A potential solution to this issue is to separate these radioisotopes from the bulk of the UNF and recycle them as fuel in advanced nuclear reactors. These separations can be achieved using electrochemical reprocessing, which employs electrochemical conversion and electrodeposition in a high-temperature molten salt electrolyte medium to separate the actinides from UNF. In this work, we review the current status, fundamental challenges, and future prospects of electrochemical reprocessing as they relate to UNF recycling.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Methods—Design Guidelines for Tubular Flow-through Electrodes for Use in Electroanalytical Studies of Redox Reaction Kinetics

The tubular flow-through electrode (FTE) is a facile electroanalytical tool for investigating electrochemical reaction kinetics; however, its suitability for this purpose requires careful design and operation under conditions that guarantee uniform current distribution. In this perspective article, we provide a scaling analysis of the transport and reaction processes within a tubular FTE leading to quantitative guidelines for the FTE design and operation. Two dimensionless parameters (classical Wagner number Wa I and modified Wagner number incorporating the effect of mass transport Wa II ) are utilized to compare the magnitudes of the ohmic, activation and transport resistances of the tubular FTE, and to quantify its current distribution uniformity. With the aid of analytical modeling of the current distribution, optimal ranges for these two dimensionless parameters are defined so as to ascertain uniform current distribution. Application of these guidelines to a graphite tubular FTE is shown to enable the precise determination of the charge-transfer kinetics of the ferri/ferrocyanide redox reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗