Modulating Entropic Driving Forces to Promote High Lithium Mobility in Solid Organic Electrolytes

• Published in: Chemistry of materials 2023-05, Vol.35 (9), p.3545-3554
• Main Authors: McAlpine, Jack, Bloemendal, Alex, Dahl, Jeremy E., Carlson, Robert M. K., Guzei, Ilia A., Clewett, Catherine F. M., Tkachenko, Boryslav O., Schreiner, Peter R., Gebbie, Matthew A.
• Format: Article
• Language: English
• ISSN: 0897-4756; 1520-5002
• DOI: 10.1021/acs.chemmater.3c00141

As large-scale lithium-ion battery deployment accelerates, continued use of flammable organic electrolytes exacerbates issues associated with battery fires during operation and disposal. While ionic liquid-derived electrolytes promise safe, nonflammable alternatives to carbonate electrolytes, the use of ionic liquids in batteries is hindered by poor lithium transport due to the formation of long-lived lithium–anion complexes. We report the design and characterization of novel ionic liquid-inspired organic electrolytes that leverage unique self-assembly properties of molecular diamond templates, called “diamondoids”. Combining thermodynamic characterization, vibrational and magnetic spectroscopy, and single-crystal X-ray analysis, we determine that diamondoid-functionalized cations can facilitate the formation of molecularly porous phases that resist restructuring upon dissolution of lithium salts. These electrolytes can suppress lithium–anion coordination, manifesting in substantially enhanced lithium-ion mobility in the organic ion matrix. Our results provide a new paradigm for enhancing lithium mobility in solid electrolytes by tuning entropic self-assembly to enhance organic cation–anion interactions, suppress lithium–anion coordination, and increase lithium mobility in solid electrolytes.