Studying Transient Phenomena in Thin Films with Reinforcement Learning.

Neutron reflectometry has long been a powerful tool to study the interfacial properties of energy materials. Recently, time-resolved neutron reflectometry has been used to better understand transient phenomena in electrochemical systems. Those measurements often comprise a large number of reflectivity curves acquired over a narrow q range, with each individual curve having lower information content compared to a typical steady-state measurement. In this work, we present an approach that leverages existing reinforcement learning tools to model time-resolved data to extract the time evolution of structure parameters. By mapping the reflectivity curves taken at different times as individual states, we use the Soft Actor-Critic algorithm to optimize the time series of structure parameters that best represent the evolution of an electrochemical system. We show that this approach constitutes an elegant solution to the modeling of time-resolved neutron reflectometry data.

Unraveling the Role of Solvation and Ion Valency on Redox-Mediated Electrosorption through In Situ Neutron Reflectometry and Ab Initio Molecular Dynamics.

Solvation and ion valency effects on selectivity of metal oxyanions at redox-polymer interfaces are explored through in situ spatial-temporally resolved neutron reflectometry combined with large scale ab initio molecular dynamics. The selectivity of ReO4- vs MoO42- for two redox-metallopolymers, poly(vinyl ferrocene) (PVFc) and poly(3-ferrocenylpropyl methacrylamide) (PFPMAm) is evaluated. PVFc has a higher Re/Mo separation factor compared to PFPMAm at 0.6 V vs Ag/AgCl. In situ techniques show that both PVFc and PFPMAm swell in the presence of ReO4- (having higher solvation with PFPMAm), but do not swell in contact with MoO42-. Ab initio molecular simulations suggest that MoO42- maintains a well-defined double solvation shell compared to ReO4-. The more loosely solvated anion (ReO4-) is preferably adsorbed by the more hydrophobic redox polymer (PVFc), and electrostatic cross-linking driven by divalent anionic interactions could impair film swelling. Thus, the in-depth understanding of selectivity mechanisms can accelerate the design of ion-selective redox-mediated separation systems for transition metal recovery and recycling.

Selective cobalt and nickel electrodeposition for lithium-ion battery recycling through integrated electrolyte and interface control.

Molecularly-selective metal separations are key to sustainable recycling of Li-ion battery electrodes. However, metals with close reduction potentials present a fundamental challenge for selective electrodeposition, especially for critical elements such as cobalt and nickel. Here, we demonstrate the synergistic combination of electrolyte control and interfacial design to achieve molecular selectivity for cobalt and nickel during potential-dependent electrodeposition. Concentrated chloride allows for the speciation control via distinct formation of anionic cobalt chloride complex (CoCl42-), while maintaining nickel in the cationic form ([Ni(H2O)5Cl]+). Furthermore, functionalizing electrodes with a positively charged polyelectrolyte (i.e., poly(diallyldimethylammonium) chloride) changes the mobility of CoCl42- by electrostatic stabilization, which tunes cobalt selectivity depending on the polyelectrolyte loading. This strategy is applied for the multicomponent metal recovery from commercially-sourced lithium nickel manganese cobalt oxide electrodes. We report a final purity of 96.4 ± 3.1% and 94.1 ± 2.3% for cobalt and nickel, respectively. Based on a technoeconomic analysis, we identify the limiting costs arising from the background electrolyte, and provide a promising outlook of selective electrodeposition as an efficient separation approach for battery recycling.

Electrochemical approaches for selective recovery of critical elements in hydrometallurgical processes of complex feedstocks.

Critical minerals are essential for the ever-increasing urban and industrial activities in modern society. The shift to cost-efficient and ecofriendly urban mining can be an avenue to replace the traditional linear flow of virgin-mined materials. Electrochemical separation technologies provide a sustainable approach to metal recovery, through possible integration with renewable energy, the minimization of external chemical input, as well as reducing secondary pollution. In this review, recent advances in electrochemically mediated technologies for metal recovery are discussed, with a focus on rare earth elements and other key critical materials for the modern circular economy. Given the extreme heterogeneity of hydrometallurgically-derived media of complex feedstocks, we focus on the nature of molecular selectivity in various electrochemically assisted recovery techniques. Finally, we provide a perspective on the challenges and opportunities for process intensification in critical materials recycling, especially through combining electrochemical and hydrometallurgical separation steps.

Semiconducting Polymer Interfaces for Electrochemically Assisted Mercury Remediation.

Nanostructured polymer interfaces can play a key role in addressing urgent challenges in water purification and advanced separations. Conventional technologies for mercury remediation often necessitate large energetic inputs, produce significant secondary waste, or when electrochemical, lead to strong irreversibility. Here, we propose the reversible, electrochemical capture and release of mercury, by modulating interfacial mercury deposition through a sulfur-containing, semiconducting redox polymer. Electrodeposition/stripping of mercury was carried out with a nanostructured poly(3-hexylthiophene-2,5-diyl)-carbon nanotube composite electrode, coated on titanium (P3HT-CNT/Ti). During electrochemical release, mercury was reversibly stripped in a non-acid electrolyte with 12-fold higher release kinetics compared to nonfunctionalized electrodes. In situ optical microscopy confirmed the rapid, reversible nature of the electrodeposition/stripping process with P3HT-CNT/Ti, indicating the key role of redox processes in mediating the mercury phase transition. The polymer-functionalized system exhibited high mercury removal efficiencies (>97%) in real wastewater matrices while bringing the final mercury concentrations down to <2 µg L-1. Moreover, an energy consumption analysis highlighted a 3-fold increase in efficiency with P3HT-CNT/Ti compared to titanium. Our study demonstrates the effectiveness of semiconducting redox polymers for reversible mercury deposition and points to future applications in mediating electrochemical stripping for various environmental applications.