Unveiling the Mechanism of Mn Dissolution Through a Dynamic Cathode‐Electrolyte Interphase on LiMn2O4

Journal Article · Sun Jun 01 00:00:00 EDT 2025 · Advanced Energy Materials

DOI:https://doi.org/10.1002/aenm.202404652· OSTI ID:2572495

Ou, Wenhan; Marks, Samuel D; de Menezes, Rafael Ferreira; He, Rong; Zhang, Zihan; Sindt, Collin; Thurston, Jonathan; Jaye, Cherno; Cowie, Bruce; Thomsen, Lars; Zhuo, Zengqing; Guo, Jinghua; Yang, Wanli; Dong, Ziyue; Tenent, Robert; Sprenger, Kayla G; Toney, Michael F

Abstract Understanding the formation and evolution of the cathode‐electrolyte interphase (CEI), which forms at the interface between the cathode and electrolyte, is crucial for revealing degradation mechanisms in cathode materials, especially for developing strategies to stabilize the interphase in the strongly oxidizing conditions that evolve at high operating voltages in next‐generation Li‐ion batteries. However, The present understanding of the CEI is challenged by its complex and dynamic nature. In this work, near‐edge X‐ray absorption fine structure spectroscopy, electrochemical characterization, and reactive molecular dynamics simulations are combined to reveal a mechanism for CEI formation and evolution above model LiMn 2 O 4 (LMO) thin‐film electrodes in contact with conventional carbonate‐based electrolytes. It is found that Mn dissolution from LMO can be understood in terms of repetitive Mn 3 O 4 formation and dissolution behavior during cycling, which is closely connected to electrolyte decomposition and a key aspect of the CEI formation and growth. The behavior of the CEI in this model system offers detailed insight into the dynamic chemistry of the interphase, underscoring the important role of electrolyte composition and cathode surface structure in interphase degradation.

• Research Organization: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
• Sponsoring Organization: US Department of Energy; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Scientific User Facilities Division (SC-22.3 )
• Grant/Contract Number: AC02-05CH11231
• OSTI ID: 2572495
• Alternate ID(s): OSTI ID: 2550580
• Journal Information: Advanced Energy Materials, Journal Name: Advanced Energy Materials Journal Issue: 22 Vol. 15
• Country of Publication: United States
• Language: English