Summary 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.

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.