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Investigation of fluorinated amides for solid-electrolyte interphase stabilization in Li–O₂ batteries using amide-based electrolytes (galley proof PDF)

ACS galley / line-numbered proof PDF for the fluorinated-amide Li–O₂ electrolyte and Li-anode SEI study; scientific content matches the version-of-record summarized on 2013bryantsev-venue-jp402844r.

Evidence and attribution

Authority of statements

This corpus PDF is a galley proof. For authoritative pagination and final copy-edited wording, use the published article (doi above) and 2013bryantsev-venue-jp402844r.

Summary

N,N-dialkyl amides such as DMA are attractive solvents for Li–O₂ cathode chemistry relative to carbonates and glymes, but they do not inherently passivate Li metal against sustained electrolyte reaction. The work benchmarks fluorinated amide formulations—notably N,N-dimethyltrifluoroacetamide (DMTFA)—using symmetric Li/electrolyte/Li cells, electrochemical impedance spectroscopy (EIS), and cycling, combined with quantum-chemistry arguments and XPS. α-Fluorinated amides are argued to reduce toward LiF-rich SEI components; XPS supports fluoride after DMTFA exposure. A 2% DMTFA additive in LiTFSI/DMA is reported to improve Li anode behavior in a rechargeable Li–O₂ demonstration context.

Methods

Electrochemistry (symmetric Li cells). The Experimental section (see pdf_path) reports symmetric Li / electrolyte / Li cells with electrochemical impedance spectroscopy (EIS) and galvanostatic Li stripping–plating to compare interfacial impedance and polarization for several fluorinated N,N-dialkyl amide solvents against N,N-dimethylacetamide (DMA) baselines, using LiTFSI and (where noted) LiClO₄ at concentrations given in the article.

Surface analysis. X-ray photoelectron spectroscopy (XPS) is used on Li foils exposed to selected amide electrolytes to probe F-containing SEI components, including after DMTFA exposure.

1 — MD application (atomistic dynamics). N/A — this publication’s core evidence is electrochemistry, quantum chemistry, and XPS; no atomistic MD production protocol is summarized in the indexed galley excerpt (normalized/extracts/2013bryantsev-venue-research_p1-2.txt).

2 — Force-field training. N/A — not a ReaxFF (or other empirical FF) parameterization study.

3 — Static QM / DFT. The Abstract states quantum chemical calculations on reduction of α-fluorinated amides on Li toward insoluble LiF, described qualitatively as proceeding with little or no activation energy (exact barrier values and transition-state details should be read from the full article PDF). Functional: N/A — not stated in the p1–2 galley extract on file. Dispersion correction: N/A — not stated in the excerpt. Basis set (and any plane-wave/PAW choices): N/A — not stated in the excerpt. k-point / k-mesh sampling: N/A — not stated in the excerpt. Confirm all QM settings against pdf_path or 2013bryantsev-venue-jp402844r. Structures / pathways: reduction of α-fluorinated alkyl amides at Li surfaces toward LiF-forming chemistry (abstract-level framing in the extract). Properties computed: reduction energetics / barrier estimates as reported in the Computational section of the full PDF (not transcribed in the short extract).

4 — Reviews / non-simulation. N/A — primary article with mixed experiment + QM, not a review.

Findings

Among the fluorinated amides examined, LiTFSI in DMTFA shows the smallest interfacial impedance and the lowest polarization for Li dissolution/deposition in the symmetric-cell screening compared to the other solvents tested in the article. α-Fluorinated amides are computed to reduce on Li with little or no activation barrier toward LiF, and XPS on DMTFA-exposed Li supports fluoride-rich interfacial composition versus purely organic-fluoride scenarios without LiF dominance. A practical additive formulation (0.5 M LiTFSI in 98% DMA / 2% DMTFA) is reported to stabilize Li cycling in a rechargeable Li–O₂ demonstration relative to DMA alone. Limitations / outlook: proof PDFs can differ from the final version-of-record text; external citations should follow published pagination on 2013bryantsev-venue-jp402844r. Corpus honesty: this slug tracks papers/Bryantsev_FluorAmides_JPC_galley.pdf as a galley duplicate of the same DOI; numerical tables and PDF locators should be taken from pdf_path or the sibling VOR page, not invented here.

Limitations

Proof PDFs can differ slightly from the final edited article; cite the published DOI for external scholarship. Full experimental detail and figure numbering align with 2013bryantsev-venue-jp402844r.

Relevance to group

Adri C. T. van Duin is a co-author; duplicate ingest documents acquisition of the galley-stage bytes for the same DOI.

Citations and evidence anchors

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