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To address these fundamental limitations, the rational design and synthesis of a novel electrolyte additive is reported here, guided by the lattice matching principle, in which thioctic acid (TA) is covalently grafted onto an Anderson\u2010type polyoxometalate (POM). During electrochemical operation, TA moieties selectively adsorb onto the Zn anode surface and undergo in situ electrochemical polymerization. Due to the Zn\u2013S interaction, Zn\n                    <jats:sup>2+<\/jats:sup>\n                    preferentially bind to the sulfur rich polymer chains with a periodic distance of 4.62 \u00c5 for S\u00b7\u00b7\u00b7S, which is perfect in agreement with the distance of zinc atoms (4.55 \u00c5) along [10] direction within (002) crystal plane, thereby inducing the atomic level deposition of Zn\n                    <jats:sup>2+<\/jats:sup>\n                    . The Zn||I\n                    <jats:sub>2<\/jats:sub>\n                    cell exhibits outstanding longevity, retaining stable performance for more than 20\u00a0000 cycles at 10 A g\n                    <jats:sup>\u22121<\/jats:sup>\n                    . Furthermore, a pouch battery with 1.6 Ah capacity retains over 99% of its initial capacity after 325 cycles. Remarkably, even at an ultralow concentration of 0.001%, the prepared electrolyte additive can enhance cycling stability. Through this work, an ultra\u2010trace additive\u2010enabled, atomic\u2010scale interfacial engineering paradigm for AZIBs is established.\n                  <\/jats:p>","DOI":"10.1002\/anie.5605595","type":"journal-article","created":{"date-parts":[[2026,9,9]],"date-time":"2026-09-09T03:46:36Z","timestamp":1788925596000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Ultra\u2010Trace Electrolyte Additives for Ah\u2010Level Zinc\u2010Ion Batteries Through Lattice\u2010Matching Strategy"],"prefix":"10.1002","author":[{"given":"Shuangyu","family":"Wu","sequence":"first","affiliation":[{"name":"State Key Laboratory of Supramolecular Structure and Materials College of Chemistry Jilin University  Changchun China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Fengxue","family":"Duan","sequence":"additional","affiliation":[{"name":"Key Laboratory of Physics and Technology for Advanced Batteries (Ministry of Education), College of Physics Jilin University  Changchun China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Junpeng","family":"Li","sequence":"additional","affiliation":[{"name":"Key Laboratory of Physics and Technology for Advanced Batteries (Ministry of Education), College of Physics Jilin University  Changchun China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Junjie","family":"Ba","sequence":"additional","affiliation":[{"name":"Key Laboratory of Physics and Technology for Advanced Batteries (Ministry of Education), College of Physics Jilin University  Changchun China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0464-6610","authenticated-orcid":false,"given":"Yizhan","family":"Wang","sequence":"additional","affiliation":[{"name":"Key Laboratory of Physics and Technology for Advanced Batteries (Ministry of Education), College of Physics Jilin University  Changchun China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0727-9764","authenticated-orcid":false,"given":"Bao","family":"Li","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Supramolecular Structure and Materials College of Chemistry Jilin University  Changchun China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4735-8558","authenticated-orcid":false,"given":"Lixin","family":"Wu","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Supramolecular Structure and Materials College of Chemistry Jilin University  Changchun 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