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Herein, we propose a catalytic strategy via \u201cconfinement\u2010pyrolysis\u201d that restructures this static reaction into a dynamic \u201csolid\u2010liquid\u2010solid\u201d pathway. By employing a hierarchical porous framework with atomically dispersed metal sites, the conversion kinetics of sodium polysulfides (NaPSs) are dramatically accelerated. This reconstruction enables continuous liquid\u2010phase intermediates and circumvents the high diffusion barriers of solid\u2010state reactions, as confirmed by density functional theory (DFT) calculations. By simulating long\u2010term cycling through controlled Na\n                    <jats:sub>2<\/jats:sub>\n                    S deposition, we employed local dipole moment change (\n                    <jats:italic>\u0394\u03bc<\/jats:italic>\n                    ) tracking to reveal the exceptional electronic structure stability and effective lowering of key energy barriers during long\u2010term cycling. As a result, the Fe\u2010N\u2010C\/S cathode exhibits outstanding electrochemical performance, delivering a reversible capacity of 799 mAh g\n                    <jats:sup>\u22121<\/jats:sup>\n                    at 1 Ag\n                    <jats:sup>\u22121<\/jats:sup>\n                    with a capacity decay rate of 0.075% per cycle, and exhibiting an ultralow capacity decay rate of 0.024% per cycle over 2000 cycles at 2 Ag\n                    <jats:sup>\u22121<\/jats:sup>\n                    . This work elucidates that redox\u2010pathway reconstruction is a pivotal strategy to overcome the inherent kinetic limitations of the conventional mode in carbonate\u2010based Na\u2500S batteries.\n                  <\/jats:p>","DOI":"10.1002\/anie.5480004","type":"journal-article","created":{"date-parts":[[2026,8,5]],"date-time":"2026-08-05T12:18:20Z","timestamp":1785932300000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Redox\u2010Pathway Reconstruction in Carbonate Electrolyte to Achieve Durable Na\u2500S Battery"],"prefix":"10.1002","volume":"65","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-4388-6561","authenticated-orcid":false,"given":"Mengting","family":"Liu","sequence":"first","affiliation":[{"name":"Center of Nanomaterials for Renewable Energy State Key Laboratory of Electrical Insulation and Power Equipment School of Electrical Engineering Xi'an Jiaotong University  Xi'an Shaanxi P.R. 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