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Inspired by polycarboxylate ether (PCE) superplasticizers in cement, we demonstrate phosphonate\u2010functionalized PCE (P\u2010PCE) could overcome both limitations. The electron\u2010rich \u2010PO\n                    <jats:sub>3<\/jats:sub>\n                    <jats:sup>2\u2013<\/jats:sup>\n                    groups could liberate Li\n                    <jats:sup>+<\/jats:sup>\n                    from the strong Li\n                    <jats:sup>+<\/jats:sup>\n                    \u2010PEO chelation and promote efficient salt dissociation without trapping Li\n                    <jats:sup>+<\/jats:sup>\n                    . Instead, they facilitate rapid Li\n                    <jats:sup>+<\/jats:sup>\n                    migration through a unique multi\u2010Li\n                    <jats:sup>+<\/jats:sup>\n                    coordination mechanism, where the electrostatic repulsion among multiple Li\n                    <jats:sup>+<\/jats:sup>\n                    ions coordinated to a single \u2010PO\n                    <jats:sub>3<\/jats:sub>\n                    <jats:sup>2\u2013<\/jats:sup>\n                    destabilizes solvation and promotes rapid Li\n                    <jats:sup>+<\/jats:sup>\n                    hopping between adjacent sites. Meanwhile, P\u2010PCE suppresses PEO crystallization and, through multi\u2010Li\n                    <jats:sup>+<\/jats:sup>\n                    coordination, induces a more extended conformation of PEO, which fosters high\u2010entropy Li\n                    <jats:sup>+<\/jats:sup>\n                    coordination environments involving TFSI\n                    <jats:sup>\u2013<\/jats:sup>\n                    , ether oxygens, and \u2010PO\n                    <jats:sub>3<\/jats:sub>\n                    <jats:sup>2\u2013<\/jats:sup>\n                    in transient combinations, promoting long\u2010range Li\n                    <jats:sup>+<\/jats:sup>\n                    transport. The simultaneously enhanced Li\n                    <jats:sup>+<\/jats:sup>\n                    concentration and mobility lead to a high ionic conductivity (1.7 \u00d7 10\n                    <jats:sup>\u22124<\/jats:sup>\n                    S\u00a0cm\n                    <jats:sup>\u22121<\/jats:sup>\n                    , 30\u00b0C) without adding liquid plasticizers. Correspondingly, Li||LiFePO\n                    <jats:sub>4<\/jats:sub>\n                    cells deliver high capacities of 140.6\u00a0mAh\u00a0g\n                    <jats:sup>\u22121<\/jats:sup>\n                    at 0.5 C and 119.7\u00a0mAh g\n                    <jats:sup>\u22121<\/jats:sup>\n                    at 1 C (30\u00b0C). This work provides a simple yet effective strategy for developing high\u2010performance solid\u2010state batteries and molecular\u2010level insights for rational polymer electrolyte designs.\n                  <\/jats:p>","DOI":"10.1002\/adma.75158","type":"journal-article","created":{"date-parts":[[2026,9,28]],"date-time":"2026-09-28T07:37:32Z","timestamp":1790581052000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Multi\u2010Li\n                    <sup>+<\/sup>\n                    Coordination for Superior Room\u2010Temperature Ionic Conductivity in PEO Solid Electrolytes"],"prefix":"10.1002","author":[{"given":"Hengming","family":"Yan","sequence":"first","affiliation":[{"name":"Key Laboratory of Low\u2010Carbon and Green Agriculture Chemistry in Universities of Shandong College of Chemistry and Material Science Shandong Agricultural University  Tai'an Shandong 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