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However, insufficient cycling stability is the core bottleneck constraining the widespread application of sodium-ion batteries (SIBs). Herein, we propose a synergistic strategy that combines non-stoichiometry with Fe2+ doping to construct Na3.4Co2.4\u2013xFex(PO4)1.4P2O7 (NCFPP-x), which not only enhances phase purity but also improves material stability. Through ex situ electrochemical impedance spectroscopy-distribution of relaxation times and galvanostatic intermittent titration technique analyses, it is demonstrated that Fe doping leads to the reduced charge transfer impedance and enhanced Na+ diffusion coefficient. The in situ XRD characterization results demonstrate a highly reversible incomplete solid-solution reaction mechanism during the Na+ intercalation and deintercalation processes. The NCFPP-1.2||Hard carbon (HC) full cell assembled with an HC anode delivers an energy density of 325 Wh kg\u20131, retaining 80.0% after 200 cycles. The present work offers important theoretical basis and experimental support for the advancement of high-voltage polyanion-type cathode materials.<\/jats:p>","DOI":"10.1021\/acsami.6c14641","type":"journal-article","created":{"date-parts":[[2026,9,30]],"date-time":"2026-09-30T20:02:34Z","timestamp":1790798554000},"page":"55148-55157","source":"Crossref","is-referenced-by-count":0,"title":["Fe-Doped Non-stoichiometric Na3.4Co2.4(PO4)1.4P2O7 Cathode for High-Energy-Density Sodium-Ion Batteries"],"prefix":"10.1021","volume":"18","author":[{"given":"Canfu","family":"Zhang","sequence":"first","affiliation":[{"name":"Hubei University , , ,","place":["Wuhan, China, 430062"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yuqi","family":"Chen","sequence":"additional","affiliation":[{"name":"Hubei University of Technology , , ,","place":["Wuhan, China, 430068"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jinbo","family":"Ye","sequence":"additional","affiliation":[{"name":"Hubei University , , ,","place":["Wuhan, China, 430062"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hao","family":"Cheng","sequence":"additional","affiliation":[{"name":"Hubei University , , ,","place":["Wuhan, China, 430062"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Bowen","family":"Yang","sequence":"additional","affiliation":[{"name":"Hubei University , , ,","place":["Wuhan, China, 430062"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0002-5808-7893","authenticated-orcid":true,"given":"Changwei","family":"Shi","sequence":"additional","affiliation":[{"name":"Wuhan Institute of Technology , , ,","place":["Wuhan, China, 430205"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ting","family":"Zhu","sequence":"additional","affiliation":[{"name":"Wuhan Textile University , , ,","place":["Wuhan, China, 430200"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3681-3148","authenticated-orcid":true,"given":"Ping","family":"Hu","sequence":"additional","affiliation":[{"name":"Hubei University , , ,","place":["Wuhan, China, 430062"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yongming","family":"Hu","sequence":"additional","affiliation":[{"name":"Hubei University , , ,","place":["Wuhan, China, 430062"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,30]]},"reference":[{"issue":"4","key":"2026101406080297200_cit1","doi-asserted-by":"publisher","first-page":"18013","DOI":"10.1038\/natrevmats.2018.13","article-title":"A Cost and Resource Analysis of Sodium-Ion Batteries","volume":"3","author":"Vaalma","year":"2018","journal-title":"Nat. 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