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However, vanadium dissolution is often caused by lattice distortion and structural collapse during Ca2+ insertion\/extraction. Herein, a Rb-doped VO2 (RbVO) material was synthesized via a facile hydrothermal method, which achieved a high cycling stability in ACIBs. Experimental and theoretical calculations indicated that Rb selectively occupied the interstitial sites of the VO2 lattice, significantly expanded the lattice, and induced a high concentration of oxygen vacancies. The unique defect-associated structure suppresses vanadium dissolution by strengthening the V\u2013O covalent network and thus enhances structural stability. Importantly, Rb doping improved Ca2+ diffusion kinetics by reducing the diffusion energy barrier from 2.74 to 1.95 eV. As expected, the RbVO cathode delivered a reversible specific capacity of 186.28 mA h g\u20131 at 0.1 A g\u20131 and achieved a capacity retention of 99.69% after 800 cycles at 2.0 A g\u20131. The experimental results combined with spectroscopy characterization elucidated that the RbVO cathode experienced reversible changes in lattice parameters and the stabilization of vanadium valence states during the Ca2+ insertion\/extraction process. This study offers a comprehensive understanding of the fabrication of high-stability vanadium-based cathode materials for ACIBs.<\/jats:p>","DOI":"10.1021\/acsami.6c12757","type":"journal-article","created":{"date-parts":[[2026,9,24]],"date-time":"2026-09-24T19:02:07Z","timestamp":1790276527000},"page":"53430-53439","source":"Crossref","is-referenced-by-count":0,"title":["Rb-Doped VO2 Enhanced Structural Stability for Aqueous Calcium-Ion Batteries"],"prefix":"10.1021","volume":"18","author":[{"given":"Xiaolei","family":"Sun","sequence":"first","affiliation":[{"name":"Guilin University of Technology , , ,","place":["Guilin, China, 541004"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0007-9305-2094","authenticated-orcid":true,"given":"Haining","family":"You","sequence":"additional","affiliation":[{"name":"Guilin University of Technology , , ,","place":["Guilin, China, 541004"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Cheng","family":"Yang","sequence":"additional","affiliation":[{"name":"Guilin University of Technology , , ,","place":["Guilin, China, 541004"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zubang","family":"Liu","sequence":"additional","affiliation":[{"name":"Guilin University of Technology , , ,","place":["Guilin, China, 541004"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yongkang","family":"Liu","sequence":"additional","affiliation":[{"name":"Guilin University of Technology , , ,","place":["Guilin, China, 541004"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8554-2698","authenticated-orcid":true,"given":"Yuanli","family":"Liu","sequence":"additional","affiliation":[{"name":"Guilin University of Technology , , ,","place":["Guilin, China, 541004"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0008-9462-3482","authenticated-orcid":true,"given":"Yaxiong","family":"Tian","sequence":"additional","affiliation":[{"name":"Guilin University of Technology , , ,","place":["Guilin, China, 541004"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,24]]},"reference":[{"issue":"18","key":"2026100711090009500_cit1","doi-asserted-by":"publisher","first-page":"8980","DOI":"10.1039\/d4cs00474d","article-title":"Interfacial Chemistry in Multivalent Aqueous Batteries: Fundamentals, Challenges, and Advances","volume":"53","author":"Ju","year":"2024","journal-title":"Chem. 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