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Here, we present a precursor-level molecular engineering strategy that simultaneously regulates sodium desolvation and interphase chemistry in HC. An iodine-mediated oxidative cross-linking process converts starch into spherical HC with uniformly distributed ultramicropores and carbonyl-rich surfaces. These nanoconfined pores are proposed to act as molecular sieves, preferentially excluding bulky solvent molecules while allowing PF\n                    <jats:sub>6<\/jats:sub>\n                    <jats:sup>\u2212<\/jats:sup>\n                    -coordinated Na\n                    <jats:sup>+<\/jats:sup>\n                    access, thereby favoring anion-enriched electrolyte structures under confinement. Surface carbonyls exhibit strong PF\n                    <jats:sub>6<\/jats:sub>\n                    <jats:sup>\u2212<\/jats:sup>\n                    affinity, which may promote fluorine-rich inorganic interphases on pore surfaces. The synergistic effects of anion-selective adsorption and confined desolvation are suggested to favor thin and robust NaF-rich interphases at external surfaces and within nanoconfined pore regions, contributing to reversible interfacial reactions and rapid Na\n                    <jats:sup>+<\/jats:sup>\n                    storage kinetics. Consequently, the HC delivers an ICE of 88.4%, a reversible capacity of 352.9\u2009mAh g\n                    <jats:sup>\u22121<\/jats:sup>\n                    at 0.1C, excellent rate capability (288.9\u2009mAh g\n                    <jats:sup>\u22121<\/jats:sup>\n                    at 5C), and 95.6% capacity retention over 200 cycles. This work offers a molecular-level design paradigm integrating efficiency, capacity, and kinetics in HC anodes.\n                  <\/jats:p>","DOI":"10.1007\/s40820-026-02300-x","type":"journal-article","created":{"date-parts":[[2026,7,27]],"date-time":"2026-07-27T06:26:58Z","timestamp":1785133618000},"update-policy":"https:\/\/doi.org\/10.1007\/springer_crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Ultramicropore-Confined Solvation and Interphase Regulation Unlock High-Performance Hard Carbon Anodes for Sodium-Ion Batteries"],"prefix":"10.1007","volume":"19","author":[{"given":"Shunyuan","family":"Tan","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhiyuan","family":"Cheng","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jiahao","family":"Xing","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jingkai","family":"Gao","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zimo","family":"Huang","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hongshuai","family":"Hou","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhongliang","family":"Tian","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yanqing","family":"Lai","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jie","family":"Li","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Simin","family":"Li","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xiaobo","family":"Ji","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"297","published-online":{"date-parts":[[2026,7,27]]},"reference":[{"issue":"17","key":"2300_CR1","doi-asserted-by":"publisher","first-page":"1703268","DOI":"10.1002\/aenm.201703268","volume":"8","author":"D Saurel","year":"2018","unstructured":"D. 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