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However, their intrinsic symmetric electronic structure restricts intermetallic electron transfer, leading to unbalanced polysulfides adsorption\u2212desorption and thus limited catalytic conversion. Herein, we construct an asymmetric Co homonuclear DAC via sulfur coordination (CoDAC\u2010S\n                    <jats:sub>1<\/jats:sub>\n                    N\n                    <jats:sub>5<\/jats:sub>\n                    ). Theoretical calculations reveal that the symmetry\u2010broken structure induces mild electron delocalization and charge redistribution. This electronic modulation contributes to cooperative yet differentiated roles of the two Co sites governed by their\n                    <jats:italic>e<\/jats:italic>\n                    <jats:sub>g<\/jats:sub>\n                    \/\n                    <jats:italic>t<\/jats:italic>\n                    <jats:sub>2g<\/jats:sub>\n                    ratios, with one site strengthening polysulfide anchoring while the other promotes S\u2500S bond activation. This dual\u2010site synergy effectively overcomes the intrinsic trade\u2010off between adsorption strength and catalytic activity, leading to accelerated polysulfide conversion kinetics and improved reaction reversibility. As a result, CoDAC\u2010S\n                    <jats:sub>1<\/jats:sub>\n                    N\n                    <jats:sub>5<\/jats:sub>\n                    delivers outstanding cycling stability over 65 cycles in Ah\u2010level pouch cells and achieves an initial energy density of 567.8\u00a0Wh\u00a0kg\n                    <jats:sub>total<\/jats:sub>\n                    <jats:sup>\u22121<\/jats:sup>\n                    at a low electrolyte\u2010to\u2010sulfur ratio of 2.1\u00a0\u00b5L mg S\n                    <jats:sup>\u22121<\/jats:sup>\n                    . This work establishes symmetry breaking as a key design principle for homonuclear DACs, providing mechanistic insights into the synergistic enhancement of catalytic activity and stability in Li\u2212S systems.\n                  <\/jats:p>","DOI":"10.1002\/adma.74358","type":"journal-article","created":{"date-parts":[[2026,7,30]],"date-time":"2026-07-30T10:23:55Z","timestamp":1785407035000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Asymmetric Electronic Configuration for Sustainable Lithium\u2013Sulfur Batteries"],"prefix":"10.1002","volume":"38","author":[{"given":"Jia","family":"Yuan","sequence":"first","affiliation":[{"name":"School of Chemistry and Chemical Engineering Shandong University  Jinan China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Peng","family":"Wang","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Shandong University  Jinan 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