Abstract
Covalent organic frameworks containing periodic redox-active motifs and conjugation structures are booming as competitive negative electrodes for ammonium-ion batteries. Introducing substantial single-electron active motifs linked by dynamic imine bonds can increase their capacity; however, this design is constrained by suboptimal single-electron redox efficiency and insufficient linkage stability. Here we unlock a multiple two-electron-transfer nitrobenzothiadiazole covalent organic framework via integrating alkynyl benzenes and nitro-functionalized four-electron benzothiadiazoles. The high degree of π-electron sp-conjugation along alkynyl linkages and strong electron-drawing effect of nitrobenzothiadiazole motifs in nitrobenzothiadiazole covalent organic framework promise high NH4+ accessibility of multi-two-electron nitro/thiazole sites (95.2% utilization) with a lower activation energy (25.93 vs. 35.99 kJ mol−1 of benzothiadiazole covalent organic framework).The fast octadeca-H-bonded NH4+ coordination in nitrobenzothiadiazole units liberates a high specific capacity of 317 mAh g−1 for nitrobenzothiadiazole covalent organic framework negative electrode. The alkynyl-bridged π-conjugation network establishes structural anti-dissolution to enable a cycling durability of 70,000 cycles. Paired with high-voltage Prussian blue analogue positive electrode, the ammonium-ion full battery delivers a specific energy of 86.1 Wh kg−1 (based on total active material mass) and a lifespan of 25,000 cycles. This work extends the design landscape of high-performance covalent organic frameworks for advanced ammonium-ion batteries.
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Acknowledgements
This work is financially supported by the National Natural Science Foundation of China (No. 22272118, M.L.; NO. 22172111, L.G.; and NO. 22309134, Z.S.), the Shanghai Rising-Star Program (23YF1449200, Z.S.), the Zhejiang Provincial Science and Technology Project (NO. 2022C01182, Y.L.), and the Fundamental Research Funds for the Central Universities (Z.S.).
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Y.C. and Z.S. conceived the idea and designed the project. L.G. and M.L. supervised the experiments and edited the paper. Y.C., Y.Q., C. H., L.M., and Y. L. performed the data processing and analysis. Y.C. and D. Z. contributed to the theoretical simulations. Y.C., Z.S., L.G. and M.L. contributed to the manuscript review. All authors discussed the results and contributed to the completion of the manuscript.
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Chen, Y., Zhang, D., Qin, Y. et al. Multi-electron nitrobenzothiadiazole sp-conjugated-alkynyl covalent organic frameworks for ammonium-ion batteries. Nat Commun (2026). https://doi.org/10.1038/s41467-026-70370-x
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DOI: https://doi.org/10.1038/s41467-026-70370-x
