Anionic Effects on Concentrated Aqueous Lithium Ion Dynamics

• Published in: The journal of physical chemistry letters Vol. 15; no. 19; pp. 5076 - 5087
• Main Authors: Felsted, Robert G., Graham, Trent R., Zhao, Yatong, Bazak, J. David, Nienhuis, Emily T., Pauzauskie, Peter J., Joly, Alan G., Pearce, Carolyn I., Wang, Zheming, Rosso, Kevin M.
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 16-05-2024
• Subjects: 2D IR; anions; concentrated electrolyte; dynamics; ion-pair; ions; lithium; Physical Insights into Materials and Molecular Properties; salts; solution chemistry; viscosity
• ISSN: 1948-7185; 1948-7185
• DOI: 10.1021/acs.jpclett.4c00585

The dynamics, orientational anisotropy, diffusivity, viscosity, and density were measured for concentrated lithium salt solutions, including lithium chloride (LiCl), lithium bromide (LiBr), lithium nitrite (LiNO2), and lithium nitrate (LiNO3), with methyl thiocyanate as an infrared vibrational probe molecule, using two-dimensional infrared spectroscopy (2D IR), nuclear magnetic resonance (NMR) spectroscopy, and viscometry. The 2D IR, NMR, and viscosity results show that LiNO2 exhibits longer correlation times, lower diffusivity, and nearly 4 times greater viscosity compared to those of the other lithium salt solutions of the same concentration, suggesting that nitrite anions may strongly facilitate structure formation via strengthening water–ion network interactions, directly impacting bulk solution properties at sufficiently high concentrations. Additionally, the LiNO2 and LiNO3 solutions show significantly weakened chemical interactions between the lithium cations and the methyl thiocyanate when compared with those of the lithium halide salts.