Reversible multivalent carrier redox exceeding intercalation capacity boundary
Abstract Compared with widely established monovalent-ion batteries, aqueous multivalent-ion batteries promise higher capacity release by achieving multiple electron-transfer events per ion intercalation in the host material. Despite plausibility, this high-capacity dream is untenable with the total...
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| Format: | Article |
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Nature Portfolio
2025-01-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-55386-5 |
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| author | Yuanhe Sun Rui Qi Qi Lei Wei Zhang Haitao Li Mengru Lin Hao Shi Jianrong Zeng Wen Wen Yi Gao Xiaolong Li Chunyi Zhi Daming Zhu |
| author_facet | Yuanhe Sun Rui Qi Qi Lei Wei Zhang Haitao Li Mengru Lin Hao Shi Jianrong Zeng Wen Wen Yi Gao Xiaolong Li Chunyi Zhi Daming Zhu |
| author_sort | Yuanhe Sun |
| collection | DOAJ |
| description | Abstract Compared with widely established monovalent-ion batteries, aqueous multivalent-ion batteries promise higher capacity release by achieving multiple electron-transfer events per ion intercalation in the host material. Despite plausibility, this high-capacity dream is untenable with the total tolerable redox charge-transfer limit of the host material for all carrier species equally, which is historically assumed to depend on the material rather than the guest carrier itself, and the kinetic hysteresis induced by larger charge/radius ratios induced kinetic hysteresis further enlarges the divide. Herein, we report that copper carrier redox in vanadium sulfide (VS2) exceeds the intrinsic intercalation capacity boundary, with the highest capacity release as 675 mAh g-1 at 0.4 A g-1 among all VS2 cathodes previously reported. Operando X-ray absorption spectroscopy, operando synchrotron X-ray diffraction and composite ex situ characterization jointly demonstrated that intercalated divalent copper is preferentially involved in redox afforded extra electron transfer to form reversible monovalent copper pillars, thus not only ensuring stable topological de/intercalation with high capacity but also sustaining fast migration kinetic paths through reconfigurable pillar effects. Intercalated carrier redox reported here emphasizes the interlayer variable valence advantage of multivalent ions, providing insights into high-performance multivalent-ion storage chemistry in aqueous batteries. |
| format | Article |
| id | doaj-art-a7c723dfd1144f5ab310d42c9b8b1c01 |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-a7c723dfd1144f5ab310d42c9b8b1c012025-01-05T12:38:21ZengNature PortfolioNature Communications2041-17232025-01-0116111110.1038/s41467-024-55386-5Reversible multivalent carrier redox exceeding intercalation capacity boundaryYuanhe Sun0Rui Qi1Qi Lei2Wei Zhang3Haitao Li4Mengru Lin5Hao Shi6Jianrong Zeng7Wen Wen8Yi Gao9Xiaolong Li10Chunyi Zhi11Daming Zhu12Shanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of SciencesShanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of SciencesShanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of SciencesShanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of SciencesShanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of SciencesShanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of SciencesShanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of SciencesShanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of SciencesShanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of SciencesShanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of SciencesShanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of SciencesDepartment of Materials Science and Engineering, City University of Hong KongShanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of SciencesAbstract Compared with widely established monovalent-ion batteries, aqueous multivalent-ion batteries promise higher capacity release by achieving multiple electron-transfer events per ion intercalation in the host material. Despite plausibility, this high-capacity dream is untenable with the total tolerable redox charge-transfer limit of the host material for all carrier species equally, which is historically assumed to depend on the material rather than the guest carrier itself, and the kinetic hysteresis induced by larger charge/radius ratios induced kinetic hysteresis further enlarges the divide. Herein, we report that copper carrier redox in vanadium sulfide (VS2) exceeds the intrinsic intercalation capacity boundary, with the highest capacity release as 675 mAh g-1 at 0.4 A g-1 among all VS2 cathodes previously reported. Operando X-ray absorption spectroscopy, operando synchrotron X-ray diffraction and composite ex situ characterization jointly demonstrated that intercalated divalent copper is preferentially involved in redox afforded extra electron transfer to form reversible monovalent copper pillars, thus not only ensuring stable topological de/intercalation with high capacity but also sustaining fast migration kinetic paths through reconfigurable pillar effects. Intercalated carrier redox reported here emphasizes the interlayer variable valence advantage of multivalent ions, providing insights into high-performance multivalent-ion storage chemistry in aqueous batteries.https://doi.org/10.1038/s41467-024-55386-5 |
| spellingShingle | Yuanhe Sun Rui Qi Qi Lei Wei Zhang Haitao Li Mengru Lin Hao Shi Jianrong Zeng Wen Wen Yi Gao Xiaolong Li Chunyi Zhi Daming Zhu Reversible multivalent carrier redox exceeding intercalation capacity boundary Nature Communications |
| title | Reversible multivalent carrier redox exceeding intercalation capacity boundary |
| title_full | Reversible multivalent carrier redox exceeding intercalation capacity boundary |
| title_fullStr | Reversible multivalent carrier redox exceeding intercalation capacity boundary |
| title_full_unstemmed | Reversible multivalent carrier redox exceeding intercalation capacity boundary |
| title_short | Reversible multivalent carrier redox exceeding intercalation capacity boundary |
| title_sort | reversible multivalent carrier redox exceeding intercalation capacity boundary |
| url | https://doi.org/10.1038/s41467-024-55386-5 |
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