Thermodynamics-Driven Treatability Investigation of Energy-Storage-Related
- 1Department of Civil and Environmental Engineering
- 2Clarkson University
Abstract
Bis-perfluoroalkyl sulfonimides (bis-FASIs), widely used in lithium-ion battery electrolytes, are increasingly detected in the environment, yet their transformation and treatability remain poorly understood. Here, density functional theory (DFT) calculations were integrated with experiments to determine how molecular structure controls bis-FASIs degradation. During electrochemical oxidation (EO) and UV/sulfite (UV/S) treatment, degradation and defluorination generally increased with perfluoroalkyl-chain length, with bis(trifluoromethylsulfonyl)imide (bis-FMeSI) being the most recalcitrant homolog. Although both processes nearly completely transformed bis-FMeSI, its fluorine fate differed markedly. EO produced trifluoromethanesulfonate (TFMS) at nearly stoichiometric yield, whereas UV/S generated both TFMS and trifluoromethanesulfonamide (TfNH 2 ). Marcus-theory calculations established the redox thresholds for one-electron transfer, while electronic-structure analysis showed that oxidation and reduction generate distinct states that follow different bond-cleavage pathways. Further transformation of TFMS and TfNH 2 required redox conditions beyond those attainable within the aqueous-phase stability window, causing their accumulation and limiting defluorination. To overcome this constraint, we demonstrated a cross-media approach in which bis-FMeSI and TFMS were adsorbed from water onto granular activated carbon and subsequently destroyed by additive-free ball milling with stainless-steel media, achieving complete degradation and near-quantitative recovery of organofluorine as fluoride. This cross-media strategy provides a potential solution for PFAS resistant to aqueous-phase treatment.
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BibTeX
@misc{xu2026thermodynamicsdriven,
title = {{Thermodynamics-Driven Treatability Investigation of Energy-Storage-Related}},
author = {Xiaotian Xu and Jinyuan Zhu and Yunqiao Guan and Yang Yang},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15008806/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008806/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Thermodynamics-Driven Treatability Investigation of Energy-Storage-Related
AU - Xiaotian Xu
AU - Jinyuan Zhu
AU - Yunqiao Guan
AU - Yang Yang
PY - 2026
DA - 2026/09/14
PB - ChemRxiv
DO - 10.26434/chemrxiv.15008806/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008806/v1
AB - Bis-perfluoroalkyl sulfonimides (bis-FASIs), widely used in lithium-ion battery electrolytes, are increasingly detected in the environment, yet their transformation and treatability remain poorly understood. Here, density functional theory (DFT) calculations were integrated with experiments to determine how molecular structure controls bis-FASIs degradation. During electrochemical oxidation (EO) and UV/sulfite (UV/S) treatment, degradation and defluorination generally increased with perfluoroalkyl-chain length, with bis(trifluoromethylsulfonyl)imide (bis-FMeSI) being the most recalcitrant homolog. Although both processes nearly completely transformed bis-FMeSI, its fluorine fate differed markedly. EO produced trifluoromethanesulfonate (TFMS) at nearly stoichiometric yield, whereas UV/S generated both TFMS and trifluoromethanesulfonamide (TfNH 2 ). Marcus-theory calculations established the redox thresholds for one-electron transfer, while electronic-structure analysis showed that oxidation and reduction generate distinct states that follow different bond-cleavage pathways. Further transformation of TFMS and TfNH 2 required redox conditions beyond those attainable within the aqueous-phase stability window, causing their accumulation and limiting defluorination. To overcome this constraint, we demonstrated a cross-media approach in which bis-FMeSI and TFMS were adsorbed from water onto granular activated carbon and subsequently destroyed by additive-free ball milling with stainless-steel media, achieving complete degradation and near-quantitative recovery of organofluorine as fluoride. This cross-media strategy provides a potential solution for PFAS resistant to aqueous-phase treatment.
ER -