Solvation-guided inhibition of manganese dissolution of lithium- and manganese- rich cathode via cyclic carbonate molecular engineering

Journal Article · Thu Oct 15 00:00:00 UTC 2026 · Journal of Power Sources

DOI:https://doi.org/10.1016/j.jpowsour.2026.240769· OSTI ID:3375397

Zhu, Qijia; Xu, Jiayi (Jason); Liu, Cong; Jiang, Wei; Wang, Jing; Yang, Zhenzhen; Yang, Jingtian; Son, Seoung-Bum; Liu, Qian; Xu, Tao; Zhang, Zhengcheng

Lithium and manganese-rich (LMR) layered oxides represent a leading class of high-energy cathode materials, but their practical realization is fundamentally limited by severe manganese (Mn) dissolution, a process that triggers structural degradation and rapid capacity fade. While mitigation efforts have predominantly focused on interfacial engineering, the intrinsic contribution of bulk electrolyte solvation to this degradation pathway remains largely unexplored, primarily due to the difficulty of deconvolving its effects from concurrent cathode-electrolyte interphase (CEI) formation. Here, we report an experimental design to isolate the role of solvation. We systematically varied the electrolyte solvent solvation power by substituting the strongly coordinating ethylene carbonate (EC) with its weaker coordinating fluorinated derivatives, fluoroethylene carbonate (FEC) and trans-4,5-Difluoro-1,3-dioxolan-2-one (DFEC), while maintaining a consistent interfacial chemistry. Remarkably, the electrolyte formulated with the weakest solvent, DFEC, exhibits superior cycling stability, suppressing Mn dissolution by up to 63% relative to the conventional EC-based system. Post-mortem analysis unequivocally attributes this performance enhancement to the preservation of the LMR cathode's structural integrity, a direct consequence of mitigated Mn dissolution. This work provides conclusive evidence that modulating bulk electrolyte solvation is a potent and direct strategy for stabilizing LMR cathodes, establishing a vital design principle for next-generation battery systems.

• Research Organization: Argonne National Laboratory (ANL)
• Sponsoring Organization: National Science Foundation (NSF); US Department of Energy; USDOE Office of Energy Efficiency and Renewable Energy (EERE) - Office of Vehicle Technologies (VTO) - Battery Materials Research (BMR) Program
• Grant/Contract Number: AC02-06CH11357
• OSTI ID: 3375397
• Journal Information: Journal of Power Sources, Journal Name: Journal of Power Sources Journal Issue: 15 Vol. 689; ISSN 0378-7753
• Country of Publication: United States
• Language: English