Studying the reaction kinetics of electrolyzing lithium chloride on an antimony electrode

J Song and XY Zhang and YF Wang and SQ Guo and WT Zhou, SEPARATION AND PURIFICATION TECHNOLOGY, 377, 134436 (2025).

DOI: 10.1016/j.seppur.2025.134436

LiCl molten salt/liquid Sb is a candidate system for the separation of elements from spent nuclear fuel, where Li competes with radioactive element to deposit into Sb electrode. By combining enhanced sampling techniques with deep neural network potentials, we unravel the fundamental reduction mechanism of Li+ at the molten salt/ liquid metal interface with ab initio accuracy. Our methodology is rigorously validated by the excellent agreement between simulated (41.9 +/- 4.6J/mol/K) and experimental (45.3 +/- 4.4J/mol/K) entropy changes. The reconstructed free energy landscape reveals a direct one-step reduction pathway: Li+ ions shed their chloride solvation shell (2Cl--> 0Cl-) while simultaneously incorporating into the Sb matrix (0Sb -> 3Sb), a mechanism previously undetected experimentally. These atomic-scale insights not only resolve long-standing questions about Li+ reduction mechanisms but also establish a universal computational paradigm for investigating molten salt electrochemical systems.

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