AUTHOR=Sánchez-Diez Eduardo , Garcia Lorena , Arcelus Oier , Qiao Lixin , San Felices Leire , Carrasco Javier , Armand Michel , Martínez-Ibañez Maria , Zhang Heng TITLE=Crystal structure and cation-anion interactions of potassium (Difluoromethanesulfonyl) (trifluorome thanesulfonyl)imide JOURNAL=Frontiers in Chemistry VOLUME=11 YEAR=2023 URL=https://www.frontiersin.org/journals/chemistry/articles/10.3389/fchem.2023.1191394 DOI=10.3389/fchem.2023.1191394 ISSN=2296-2646 ABSTRACT=

Sulfonimide salts are of great interest for battery use thanks to their special properties including sufficient superior chemical/thermal stabilities, structural flexibility, etc. In particular, the hydrogen-containing sulfonimide (difluoromethanesulfonyl)(trifluoromethanesulfonyl)imide anion {[N(SO2CF2H) (SO2CF3)], DFTFSI}, stands out owing to its suppressed anion mobility and superior electrochemical properties. We herein report the structural analyses of potassium (difluoromethanesulfonyl)(trifluoromethanesulfonyl)imide {K [N(SO2CF2H) (SO2CF3)], KDFTFSI} by virtue of single crystal X-ray diffraction and computational approaches. Our results reveal that KDFTFSI crystallizes in a orthorhombic cell (space group: Pbcn) comprising of cationic and anionic layers, which is similar to the conventional sulfonimide salt, potassium bis(trifluoromethanesulfonyl)imide {K [N(SO2CF3)2], KTFSI}. Gas-phase density functional theory calculations show that the conversion from trans to cis DFTFSI anions is hindered due to the presence of stabilizing intramolecular H-bonding interactions in the trans conformer; yet interaction with K+ substantially minimizes the energy difference between the two conformers due to the formation of strong tridentate K+ coordination with oxygen atoms in the cis KDFTFSI. This work is anticipated to provide further understanding on the structure-property relations of hydrogenated sulfonimide anions, and thus inspire the structural design of new anions for battery research.