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To address this intrinsic limitation, we introduce FeF\n                    <jats:sub>3<\/jats:sub>\n                    as a multifunctional additive into the PEO\/poly(vinylidene fluoride\u2010co\u2010hexafluoropropylene) (PVDF\u2011HFP) matrix, yielding the FeF\n                    <jats:sub>3<\/jats:sub>\n                    \u2011PEOPVLi electrolyte. Fe\n                    <jats:sup>3+<\/jats:sup>\n                    ions with strong Lewis acidity competitively coordinate with the ether oxygen atoms via Fe\n                    <jats:sup>3+<\/jats:sup>\n                    \u2013O\u2013C interactions, thereby weakening the native Li\n                    <jats:sup>+<\/jats:sup>\n                    \u2013O\u2013C coordination and substantially reducing the energy barrier for Li\n                    <jats:sup>+<\/jats:sup>\n                    hopping. Concurrently, the strong electron withdrawing nature of Fe\n                    <jats:sup>3+<\/jats:sup>\n                    promotes lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) dissociation by weakening the Li\u2013N bond, increasing the concentration of free Li\n                    <jats:sup>+<\/jats:sup>\n                    ions available for ionic transport. Benefiting from these synergistic effects, the FeF\n                    <jats:sub>3<\/jats:sub>\n                    \u2011PEOPVLi electrolyte achieves high ionic conductivity of 0.13 mS cm\n                    <jats:sup>\u2212<\/jats:sup>\n                    <jats:sup>1<\/jats:sup>\n                    at 25\u00b0C. Solid\u2010state Li||LiFePO\n                    <jats:sub>4<\/jats:sub>\n                    batteries deliver discharge capacity of 120.6 mAh g\n                    <jats:sup>\u2212<\/jats:sup>\n                    <jats:sup>1<\/jats:sup>\n                    at 0.5 C at 25\u00b0C and retains 88.4% of its capacity after 1000 cycles. This work demonstrates that rational modulation of the coordination environment within PEO provides a viable and effective pathway toward high\u2011performance room\u2011temperature solid\u2011state lithium metal batteries.\n                  <\/jats:p>","DOI":"10.1002\/smtd.71118","type":"journal-article","created":{"date-parts":[[2026,10,13]],"date-time":"2026-10-13T07:17:26Z","timestamp":1791875846000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Competitive Coordination to Ether Oxygens Enables High\u2010Ionic\u2010Conductivity Solid Polymer Electrolytes at Room Temperature"],"prefix":"10.1002","author":[{"given":"Chengru","family":"Chen","sequence":"first","affiliation":[{"name":"School of Electrical and Control Engineering Xuzhou University of Technology  Xuzhou Jiangsu 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