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However, their development is plagued by sluggish reaction kinetics and poor cycling stability. Although catalysts are indispensable to mitigate these issues, achieving both low polarization and durable high\u2010rate cycling remains a longstanding challenge. Here, we engineer a cost\u2010effective copper (I) oxide (Cu\n                    <jats:sub>2<\/jats:sub>\n                    O)\u2010zinc niobate (ZnNb\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>6<\/jats:sub>\n                    ) heterostructured catalyst featuring oxygen vacancies and strong d\u2010p\u2010d interfacial orbital hybridization to overcome these bottlenecks. Multimodal in situ spectroscopies, synchrotron characterization, and computational studies reveal that this configuration constructs enriched active sites and continuous interfacial charge\u2010transfer channels, promoting the formation of finely dispersed lithium carbonate (Li\n                    <jats:sub>2<\/jats:sub>\n                    CO\n                    <jats:sub>3<\/jats:sub>\n                    ) with elongated Li\u2500O bonds. These synergetic effects accelerate CO\n                    <jats:sub>2<\/jats:sub>\n                    conversion kinetics and reduce the decomposition barrier of discharge products, enabling highly reversible cycling even under high rates. The resulting Li\u2010CO\n                    <jats:sub>2<\/jats:sub>\n                    battery thus operates stably for 5400\u00a0h at 100\u00a0mA g\n                    <jats:sup>\u22121<\/jats:sup>\n                    and maintains a low overpotential of 1.6\u00a0V at 1000\u00a0mA g\n                    <jats:sup>\u22121<\/jats:sup>\n                    , with a pouch cell retaining robust cyclability over 484 cycles at the same high rate, demonstrating record performance that surpasses prior reported results. This work opens a promising pathway for designing high\u2010performance catalysts for sustainable batteries with robust performance.\n                  <\/jats:p>","DOI":"10.1002\/anie.7187088","type":"journal-article","created":{"date-parts":[[2026,5,20]],"date-time":"2026-05-20T08:42:21Z","timestamp":1779266541000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Fast\u2010Kinetic and Stable Li\u2010CO\n                    <sub>2<\/sub>\n                    Batteries Driven by an Oxygen\u2010Defective Cu\n                    <sub>2<\/sub>\n                    O\u2010ZnNb\n                    <sub>2<\/sub>\n                    O\n                    <sub>6<\/sub>\n                    Catalyst Through d\u2010p\u2010d Orbital Hybridization"],"prefix":"10.1002","volume":"65","author":[{"given":"Shasha","family":"Xiao","sequence":"first","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering, Beijing Key Laboratory of Electrochemical Process and Technology of Materials, National Engineering Research Center for Fuel Cell and Hydrogen Source Technology Beijing University of Chemical Technology  Beijing P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1807-4246","authenticated-orcid":false,"given":"Ying","family":"Xiao","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering, Beijing Key Laboratory of Electrochemical Process and Technology of Materials, National Engineering Research Center for Fuel Cell and Hydrogen Source Technology Beijing University of Chemical Technology  Beijing P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yu","family":"Yang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering, Beijing Key Laboratory of Electrochemical Process and Technology of Materials, National Engineering Research Center for Fuel Cell and Hydrogen Source Technology Beijing University of Chemical Technology  Beijing P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xinyu","family":"Wang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering, Beijing Key Laboratory of Electrochemical Process and Technology of Materials, National Engineering Research Center for Fuel Cell and Hydrogen Source Technology Beijing University of Chemical Technology  Beijing P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yiming","family":"Fang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering, Beijing Key Laboratory of Electrochemical Process and Technology of Materials, National Engineering Research Center for Fuel Cell and Hydrogen Source Technology Beijing University of Chemical Technology  Beijing P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2533-4010","authenticated-orcid":false,"given":"Shimou","family":"Chen","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering, Beijing Key Laboratory of Electrochemical Process and Technology of Materials, National Engineering Research Center for Fuel Cell and Hydrogen Source Technology Beijing University of Chemical Technology  Beijing P. R. 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