Decoding Gas Evolution Pathways and Interfacial Chemistry in Layered Oxide Cathodes for Safer Sodium‐Ion Batteries
Year: 2025
Type: article
Abstract: Sodium‐ion batteries (SIBs) are attractive for the low cost and abundance of sodium. Yet, gas evolution—a critical challenge in SIBs—remains underexplored. Here, online electrochemical mass spectrometry is used to probe gas evolution in layered oxide cathodes with various compositions, cutoff voltages, dopants, and particle morphologies. Compared to LiNiO 2 (LNO), NaNiO 2 releases more gas, even at lower states of charge, due to the higher covalency of Ni─O bond caused by the more ionic Na─O bond through the inductive effect. Among Co, Mn, Al, and Mg, Mn and Mg doping suppress gas release most effectively by enhancing the metal‐oxygen bond strength. NaNi 1/3 Fe 1/3 Mn 1/3 O 2 (NFM) cathodes synthesized via coprecipitation (CP‐NFM) and solid‐state routes exhibit distinct particle morphologies; CP‐NFM exhibits more gas evolution, yet secondary particle morphology helps reduce it through differential cathode‐electrolyte reactivity between inner and outer primary particles. Among Li, Ti, Mg, and Cu doping in NFM, Li has the largest effect, reducing gas levels comparable to LNO. Nuclear magnetic resonance and X‐ray photoelectron spectroscopies reveal that electrolyte solvent decomposition mainly produces organic‐rich cathode‐electrolyte interphase (CEI) rather than soluble species. NaPF 6 salt further exacerbates cathode‐electrolyte reactions, forming surface Na 2 O species. The findings provide actionable guidance for designing safer, durable SIBs.
Source: Advanced Energy Materials
Authors: Chen Liu, Zehao Cui, Arumugam Manthiram
Institution: The University of Texas at Austin
Language: English
Subfield: Electrical and Electronic Engineering
Field: Engineering
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $5,790
OpenAlex ID: W4416100316