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Here, we report a thermodynamically guided entropy\u2010vacancy engineering strategy to reconcile this fundamental asymmetry by constructing a medium\u2010entropy Na\n                    <jats:sub>3<\/jats:sub>\n                    Fe\n                    <jats:sub>0.6<\/jats:sub>\n                    Al\n                    <jats:sub>0.4<\/jats:sub>\n                    V(PO\n                    <jats:sub>4<\/jats:sub>\n                    )\n                    <jats:sub>3<\/jats:sub>\n                    (ME\u2010NF\n                    <jats:sub>0.6<\/jats:sub>\n                    A\n                    <jats:sub>0.4<\/jats:sub>\n                    VP) cathode. Machine\u2010learning potential calculations reveal that selective iron incorporation induces abundant oxygen vacancies, which construct continuous Na\n                    <jats:sup>+<\/jats:sup>\n                    diffusion pathways and accelerate interfacial charge transfer, while aluminium incorporation modulates the local coordination environment to stabilize highly redox\u2010active sites. The enthalpy\u2010entropy coupling activates the high\u2010voltage V\n                    <jats:sup>4+<\/jats:sup>\n                    \/V\n                    <jats:sup>5+<\/jats:sup>\n                    redox couple, unlocks previously inaccessible Na1 sites, and enables a highly reversible high\u2010voltage solid\u2010solution reaction with a minimal lattice expansion of only 6.28%. Consequently, ME\u2010NF\n                    <jats:sub>0.6<\/jats:sub>\n                    A\n                    <jats:sub>0.4<\/jats:sub>\n                    VP cathode delivers an exceptional cyclability over 10\u00a0000 cycles at an ultrahigh rate of 100C, and robust wide\u2010temperature application from \u201030\u00b0C to 60\u00b0C. The full SIHCs device achieves a maximum energy density of 223\u00a0Wh kg\n                    <jats:sup>\u22121<\/jats:sup>\n                    (at 44\u00a0W kg\n                    <jats:sup>\u22121<\/jats:sup>\n                    ) and retains 51\u00a0Wh kg\n                    <jats:sup>\u22121<\/jats:sup>\n                    at 5940\u00a0W kg\n                    <jats:sup>\u22121<\/jats:sup>\n                    . This work delineates a viable thermodynamic design pathway for cathode design, providing a blueprint for practical and high\u2010performance sodium\u2010ion energy\u2010storage systems.\n                  <\/jats:p>","DOI":"10.1002\/adma.75186","type":"journal-article","created":{"date-parts":[[2026,9,29]],"date-time":"2026-09-29T13:58:25Z","timestamp":1790690305000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Medium\u2010Entropy\u2010Vacancy Engineering Unlocks Energy\u2010Power Trade\u2010Off Reconciliation in Sodium\u2010Ion Hybrid Capacitors"],"prefix":"10.1002","author":[{"given":"Ziting","family":"Chen","sequence":"first","affiliation":[{"name":"State Key Laboratory of Structural Chemistry, and Fujian Provincial Key Laboratory of Materials and Techniques toward Hydrogen Energy Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences  Fuzhou Fujian China"},{"name":"College of 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