Understanding the Solvation-Dependent Properties of Cyclic Ether Multivalent Electrolytes Using High-Field NMR and Quantum Chemistry

Efforts to expand the technological capability of batteries have generated increased interest in divalent cationic systems. Electrolytes used for these electrochemical applications often incorporate cyclic ethers as electrolyte solvents; however, the detailed solvation environments within such systems are not well-understood. To foster insights into the solvation structures of such electrolytes, Ca­(TFSI)₂ and Zn­(TFSI)₂ dissolved in tetrahydrofuran (THF) and 2-methyl-tetrahydrofuran were investigated through multi-nuclear magnetic resonance spectroscopy (¹⁷O, ⁴³Ca, and ⁶⁷Zn NMR) combined with quantum chemistry modeling of NMR chemical shifts. NMR provides spectroscopic fingerprints that readily couple with quantum chemistry to identify a set of most probable solvation structures based on the best agreement between the theoretically predicted and experimentally measured values of chemical shifts. The multi-nuclear approach significantly enhances confidence that the correct solvation structures are identified due to the required simultaneous agreement between theory and experiment for multiple nuclear spins. Furthermore, quantum chemistry modeling provides a comparison of the solvation cluster formation energetics, allowing further refinement of the preferred solvation structures. It is shown that a range of solvation structures coexist in most of these electrolytes, with significant molecular motion and dynamic exchange among the structures. This level of solvation diversity correlates with the solubility of the electrolyte, with Zn­(TFSI)₂/THF exhibiting the lowest degree of each. Comparisons of analogous Ca²⁺ and Zn²⁺ solvation structures reveal a significant cation size effect that is manifested in significantly reduced cation–solvent bond lengths and thus stronger solvent bonding for Zn²⁺ relative to Ca²⁺. The strength of this bonding is further reduced by methylation of the cyclic ether ring. Solvation shells containing anions are energetically preferred in all the studied electrolytes, leading to significant quantities of contact ion pairs and consequently neutrally charged clusters. It is likely that the transport and interfacial de-solvation/re-solvation properties of these electrolytes are directed by these anion interactions. These insights into the detailed solvation structures, cation size, and solvent effects, including the molecular dynamics, are fundamentally important for the rational design of electrolytes in multivalent battery electrolyte systems.