Metal‐Free Eutectic Electrolyte with Weak Hydrogen Bonds for High‐Rate and Ultra‐Stable Ammonium‐Ion Batteries

• Published in: Advanced materials (Weinheim) 2024-02, Vol.36 (6), p.e2308210-n/a
• Main Authors: Hong, Hu, Zhu, Jiaxiong, Wang, Yiqiao, Wei, Zhiquan, Guo, Xun, Yang, Shuo, Zhang, Rong, Cui, Huilin, Li, Qing, Zhang, Dechao, Zhi, Chunyi
• Format: Article
• Language: English
• Subjects: ammonium‐ion batteries; Bonding strength; Charge transfer; Electrolytes; Electronegativity; Energy storage; eutectic electrolytes; hydrogen bond chemistry; Hydrogen bonds; Solvation; Solvents; Storage systems; Succinonitrile
• ISSN: 0935-9648; 1521-4095
• DOI: 10.1002/adma.202308210

As the need for sustainable battery chemistry grows, non‐metallic ammonium ion (NH4+) batteries are receiving considerable attention because of their unique properties, such as low cost, nontoxicity, and environmental sustainability. In this study, the solvation interactions between NH4+ and solvents are elucidated and design principles for NH4+ weakly solvated electrolytes are proposed. Given that hydrogen bond interactions dominate the solvation of NH4+ and solvents, the strength of the solvent's electrostatic potential directly determines the strength of its solvating power. As a proof of concept, succinonitrile with relatively weak electronegativity is selected to construct a metal‐free eutectic electrolyte (MEE). As expected, this MEE is able to significantly broaden the electrochemical stability window and reduce the solvent binding energy in the solvation shell, which leads to a lower desolvation energy barrier and a fast charge transfer process. As a result, the as‐constructed NH4‐ion batteries exhibit superior reversible rate capability (energy density of 65 Wh kg–1total active mass at 600 W kg–1) and unprecedent long‐term cycling performance (retention of 90.2% after 1000 cycles at 1.0 A g–1). The proposed methodology for constructing weakly hydrogen bonded electrolytes will provide guidelines for implementing high‐rate and ultra‐stable NH4+‐based energy storage systems. Hydrogen bonds dominate the solvation interaction of NH4+. Weakening the interactions between NH4+ and solvent molecules can significantly improve the rate capability and long‐term cycling performance of NH4‐ion batteries.