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Herein, a facile surface fluorination strategy is presented for Li\n                    <jats:sub>6<\/jats:sub>\n                    PS\n                    <jats:sub>5<\/jats:sub>\n                    Cl using XeF\n                    <jats:sub>2<\/jats:sub>\n                    as a solid\u2010state fluorinating agent, enabling a scalable dry process at moderate temperatures. An \u224837.3 nm\u2010thick uniform fluorinated layer is coated on an Li\n                    <jats:sub>6<\/jats:sub>\n                    PS\n                    <jats:sub>5<\/jats:sub>\n                    Cl surface, preserving 82.8% of the initial Li\n                    <jats:sup>+<\/jats:sup>\n                    conductivity (from 2.9 \u00d7 10\u207b\n                    <jats:sup>3<\/jats:sup>\n                    only to 2.4 \u00d7 10\u207b\n                    <jats:sup>3<\/jats:sup>\n                    S cm\u207b\u00b9 at 30 \u00b0C). The underlying fluorination mechanism, deduced through systematic investigations using X\u2010ray photoelectron spectroscopy, X\u2010ray Rietveld refinement, nuclear magnetic resonance, and density functional theory calculations, involves the formation of surface oxidative byproducts and F substitution within the lattice. When applied to LiNi\n                    <jats:sub>0.90<\/jats:sub>\n                    Co\n                    <jats:sub>0.05<\/jats:sub>\n                    Mn\n                    <jats:sub>0.05<\/jats:sub>\n                    O\n                    <jats:sub>2<\/jats:sub>\n                    electrodes in LiNi\n                    <jats:sub>0.90<\/jats:sub>\n                    Co\n                    <jats:sub>0.05<\/jats:sub>\n                    Mn\n                    <jats:sub>0.05<\/jats:sub>\n                    O\n                    <jats:sub>2<\/jats:sub>\n                    ||(Li\u2010In) half cells at 30 \u00b0C, the fluorinated Li\n                    <jats:sub>6<\/jats:sub>\n                    PS\n                    <jats:sub>5<\/jats:sub>\n                    Cl substantially improves the electrochemical performance, delivering superior discharge capacities (e.g., 186.9 vs 173.6\u00a0mA h g\n                    <jats:sup>\u22121<\/jats:sup>\n                    at 0.33C), capacity retention, and safety characteristics compared to unmodified Li\n                    <jats:sub>6<\/jats:sub>\n                    PS\n                    <jats:sub>5<\/jats:sub>\n                    Cl. This enhancement is attributed to the formation of a robust fluorinated cathode electrolyte interphase that mitigates Li\n                    <jats:sub>6<\/jats:sub>\n                    PS\n                    <jats:sub>5<\/jats:sub>\n                    Cl oxidation. Finally, the stable operation of a pouch\u2010type LiNi\n                    <jats:sub>0.90<\/jats:sub>\n                    Co\n                    <jats:sub>0.05<\/jats:sub>\n                    Mn\n                    <jats:sub>0.05<\/jats:sub>\n                    O\n                    <jats:sub>2<\/jats:sub>\n                    ||Li ASSB is demonstrated, highlighting the scalability of the proposed approach.\n                  <\/jats:p>","DOI":"10.1002\/adma.202416816","type":"journal-article","created":{"date-parts":[[2025,6,23]],"date-time":"2025-06-23T03:01:02Z","timestamp":1750647662000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":21,"title":["Surface Fluorination Shielding of Sulfide Solid Electrolytes for Enhanced Electrochemical Stability in All\u2010Solid\u2010State Batteries"],"prefix":"10.1002","volume":"37","author":[{"given":"Kyu Tae","family":"Kim","sequence":"first","affiliation":[{"name":"Department of Chemical and Biomolecular Engineering Yonsei University  Seoul 03722 Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jae\u2010Seung","family":"Kim","sequence":"additional","affiliation":[{"name":"Department of Materials Science and Engineering Korea Advanced Institute of Science and Technology  Daejeon 34141 Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ki Heon","family":"Baeck","sequence":"additional","affiliation":[{"name":"Department of Chemical and Biomolecular Engineering Yonsei University  Seoul 03722 Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jong Seok","family":"Kim","sequence":"additional","affiliation":[{"name":"Department of Chemical and Biomolecular Engineering Yonsei University  Seoul 03722 Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Juhyoun","family":"Park","sequence":"additional","affiliation":[{"name":"Department of Chemical and Biomolecular Engineering Yonsei University  Seoul 03722 Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Seongil","family":"Bong","sequence":"additional","affiliation":[{"name":"Department of Chemical and Biomolecular Engineering Yonsei University  Seoul 03722 Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Young Joon","family":"Park","sequence":"additional","affiliation":[{"name":"Department of Chemical and Biomolecular Engineering Yonsei University  Seoul 03722 Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yong Bae","family":"Song","sequence":"additional","affiliation":[{"name":"Department of Chemical and Biomolecular Engineering Yonsei University  Seoul 03722 Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Changhyun","family":"Park","sequence":"additional","affiliation":[{"name":"School of Energy and Chemical Engineering Ulsan 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