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Molten salt electrolysis is a vital technique to produce high-purity lanthanide metals and alloys. However, the coordination environments of lanthanides in molten salts, which heavily affect the related redox potential and electrochemical properties, have not been well elucidated. Here we explore the competitive coordination of chloride and fluoride anions towards lanthanide cations (La 3+ and Nd 3+ ) in molten LiCl-KCl-LiF-LnCl 3 salts by using electrochemical, spectroscopic , and computational approaches. Electrochemical analyses show that significant negative shifts in the reduction potential of Ln 3+ occur when F - concentration increases, indicating that the F - anions interact with Ln 3+ via substituting the coordinated Cl - anions, and confirm [LnCl x F y ] 3-x-y (y max =3) complexes are prevailing in molten salts. Spectroscopic and computational results on solution structures further reveal the competition between Cl - and F - anions, which leads to the formation of four distinct Ln(III) species: [LnCl 6 ] 3- , [LnCl 5 F] 3- , [LnCl 4 F 2 ] 3- and [LnCl 4 F 3 ] 4- . Among them, the seven-coordinated [LnCl 4 F 3 ] 4- complex possesses a low-symmetry structure evidenced by the pattern change of Raman spectra. After comparing the polarizing power (Z/r) among different metal cations, we conclude that Ln-F interaction is weaker than that between transition metal and F - ions.

Molten salt electrolysis is a vital technique to produce high-purity lanthanide metals and alloys. However, the coordination environments of lanthanides in molten salts, which heavily affect the related redox potential and electrochemical properties, have not been well elucidated. Here, the competitive coordination of chloride and fluoride anions towards lanthanide cations (La