Abstract
Conversion-type positive electrodes offer high theoretical energy density for next-generation energy storage, but their practical application is limited by severe shuttle effects and sluggish kinetics under high loadings. Achieving strong adsorption and fast redox kinetics is challenging, as the Sabatier principle implies that overly strong adsorption stabilizes intermediates and inhibits their conversion. Herein, we propose and validate an f–d orbital tag-team catalysis mechanism that overcomes this limitation within a model zinc | |iodine system. Leveraging a machine learning-guided descriptor framework, we identify cerium single-atom catalysts as an optimal catalytic center for iodine conversion, surpassing d-block analogues. Density functional theory calculations reveal a tag-team catalytic mechanism in which Ce 5 d orbitals strongly anchor iodine intermediates while near-Fermi-level Ce 4 f orbitals introduce antibonding interactions that exert tunable electronic repulsion on the I − I bond. This orbital tag-team catalysis mechanism enables simultaneous stabilization of polyiodide intermediates and facilitation of bond activation, achieving an iodine loading of 44.7 mg cm−2 with an areal capacity of 10 mAh cm−2, and a practical pouch cell capacity at a high mass loading of 115 mg cm−2. This work bridges the orbital-level catalyst design with practical performance, offering a strategy for advancing high-loading conversion-type positive electrodes in battery systems.
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All data are available in the main text and the supplementary information. Source data are provided with this paper. The VASP-format optimized structures54 of the M-N-C catalysts and the relevant adsorption intermediates, as well as code that support the findings of this study are openly available in Zenodo at https://doi.org/10.5281/zenodo.17629945. A README file is included in the repository, detailing system requirements, installation steps, and instructions for reproducing the results. Source data are provided with this paper.
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Acknowledgements
The authors acknowledge the support from the Energy Revolution S&T Program of Yulin Innovation Institute of Clean Energy (No. E411110705 to Q.H.Y) and the National Natural Science Foundation of China (No. 22379108 to C.Y., Nos. 52432005, W2521109 and 22121004 to Q.H.Y.). The authors also appreciate the funding support from the Haihe Laboratory of Sustainable Chemical Transformations, the National Industry-Education Integration Platform of Energy Storage, and the Fundamental Research Funds for the Central Universities.
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Q.-H. Yang and C. Yang conceived the idea and directed the project. M. Chen designed the experiments. M. Chen, Z. Wu, and J. Chen carried out the materials synthesis, characterization, and performance measurements. Y. He, H. Li, J. Lu, W. Wang, and L. Wang contributed to the theoretical calculations. A. Du contributed to SEM. M. Chen, Y. He, H. Li, and Z. Wu co-wrote the paper. Q.-H. Yang, C. Yang, and W. Wang revised the manuscript. All authors discussed the results and commented on the manuscript.
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Chen, M., He, Y., Li, H. et al. 4f-5d orbital tag-team catalysis empowers high-loading zinc–iodine batteries. Nat Commun (2026). https://doi.org/10.1038/s41467-026-70908-z
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DOI: https://doi.org/10.1038/s41467-026-70908-z
