Tailoring the Structural Evolution of Multi‐Electron Redox Conversions via Strong Selenium–Carbon Interaction for Robust Aqueous Copper‐Ion Batteries

Abstract Aqueous metal‐selenium batteries based on chalcogenide cathodes, despite their multi‐electron conversion‐type redox reactions and rapid kinetics, suffer from short lifespans and unclear capacity degradation mechanisms. The interfacial interactions between doped carbon and chalcogenides corr...

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Main Authors: Fan Jiang, Haoyu Peng, Yiqian Wu, Yichen Li, Zeyu Zhang, Yue Wang, Jiuqiang Li, Jing Peng, Maolin Zhai
Format: Article
Language:English
Published: Wiley 2025-04-01
Series:Advanced Science
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Online Access:https://doi.org/10.1002/advs.202417084
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author Fan Jiang
Haoyu Peng
Yiqian Wu
Yichen Li
Zeyu Zhang
Yue Wang
Jiuqiang Li
Jing Peng
Maolin Zhai
author_facet Fan Jiang
Haoyu Peng
Yiqian Wu
Yichen Li
Zeyu Zhang
Yue Wang
Jiuqiang Li
Jing Peng
Maolin Zhai
author_sort Fan Jiang
collection DOAJ
description Abstract Aqueous metal‐selenium batteries based on chalcogenide cathodes, despite their multi‐electron conversion‐type redox reactions and rapid kinetics, suffer from short lifespans and unclear capacity degradation mechanisms. The interfacial interactions between doped carbon and chalcogenides correlate closely with the electrochemical structural evolution. Hence, flower‐like Cu2−xSe wrapped with ultrathin N‐doped carbon layer (Cu2−xSe@N‐C) is synthesized via a simple γ radiation‐pyrolysis route for the first time. The Cu2−xSe@N‐C cathode displays a high‐rate performance and long‐term stability, with a respective capacity of 310.6 mAh g−1 at 20 A g−1 and a capacity retention rate of 92.9% after 30 000 cycles over 2000 h at 5 A g−1. Ex situ X‐ray diffraction and X‐ray photoelectron spectroscopy confirm the reversible Cu storage mechanism of the Cu2−xSe@N‐C cathode and the issues of volume expansion and oxidative dissolution related to the capacity degradation of the Cu2−xSe cathode. Furthermore, X‐ray absorption analysis and theoretical calculations reveal the presence of Se─C interactions between the ultrathin N‐doped carbon and Cu2−xSe. As a result, the physical and chemical dual‐protection of N‐doped carbon via Se‐C not only effectively stabilizes the structural evolution of Cu2−xSe but also endows it with faster electrode reaction kinetics.
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spelling doaj-art-1d1b67dc86f5414d94d7ab0bcd19a1622025-08-20T03:18:05ZengWileyAdvanced Science2198-38442025-04-011215n/an/a10.1002/advs.202417084Tailoring the Structural Evolution of Multi‐Electron Redox Conversions via Strong Selenium–Carbon Interaction for Robust Aqueous Copper‐Ion BatteriesFan Jiang0Haoyu Peng1Yiqian Wu2Yichen Li3Zeyu Zhang4Yue Wang5Jiuqiang Li6Jing Peng7Maolin Zhai8Beijing National Laboratory for Molecular Sciences Radiochemistry and Radiation Chemistry Key Laboratory of Fundamental Science the Key Laboratory of Polymer Chemistry and Physics of the Ministry of Education College of Chemistry and Molecular Engineering Peking University Beijing 100871 P. R. ChinaBeijing National Laboratory for Molecular Sciences Radiochemistry and Radiation Chemistry Key Laboratory of Fundamental Science the Key Laboratory of Polymer Chemistry and Physics of the Ministry of Education College of Chemistry and Molecular Engineering Peking University Beijing 100871 P. R. ChinaBeijing National Laboratory for Molecular Sciences Radiochemistry and Radiation Chemistry Key Laboratory of Fundamental Science the Key Laboratory of Polymer Chemistry and Physics of the Ministry of Education College of Chemistry and Molecular Engineering Peking University Beijing 100871 P. R. ChinaBeijing National Laboratory for Molecular Sciences Radiochemistry and Radiation Chemistry Key Laboratory of Fundamental Science the Key Laboratory of Polymer Chemistry and Physics of the Ministry of Education College of Chemistry and Molecular Engineering Peking University Beijing 100871 P. R. ChinaChemical Defense Institute Beijing 100191 P. R. ChinaBeijing National Laboratory for Molecular Sciences Radiochemistry and Radiation Chemistry Key Laboratory of Fundamental Science the Key Laboratory of Polymer Chemistry and Physics of the Ministry of Education College of Chemistry and Molecular Engineering Peking University Beijing 100871 P. R. ChinaBeijing National Laboratory for Molecular Sciences Radiochemistry and Radiation Chemistry Key Laboratory of Fundamental Science the Key Laboratory of Polymer Chemistry and Physics of the Ministry of Education College of Chemistry and Molecular Engineering Peking University Beijing 100871 P. R. ChinaBeijing National Laboratory for Molecular Sciences Radiochemistry and Radiation Chemistry Key Laboratory of Fundamental Science the Key Laboratory of Polymer Chemistry and Physics of the Ministry of Education College of Chemistry and Molecular Engineering Peking University Beijing 100871 P. R. ChinaBeijing National Laboratory for Molecular Sciences Radiochemistry and Radiation Chemistry Key Laboratory of Fundamental Science the Key Laboratory of Polymer Chemistry and Physics of the Ministry of Education College of Chemistry and Molecular Engineering Peking University Beijing 100871 P. R. ChinaAbstract Aqueous metal‐selenium batteries based on chalcogenide cathodes, despite their multi‐electron conversion‐type redox reactions and rapid kinetics, suffer from short lifespans and unclear capacity degradation mechanisms. The interfacial interactions between doped carbon and chalcogenides correlate closely with the electrochemical structural evolution. Hence, flower‐like Cu2−xSe wrapped with ultrathin N‐doped carbon layer (Cu2−xSe@N‐C) is synthesized via a simple γ radiation‐pyrolysis route for the first time. The Cu2−xSe@N‐C cathode displays a high‐rate performance and long‐term stability, with a respective capacity of 310.6 mAh g−1 at 20 A g−1 and a capacity retention rate of 92.9% after 30 000 cycles over 2000 h at 5 A g−1. Ex situ X‐ray diffraction and X‐ray photoelectron spectroscopy confirm the reversible Cu storage mechanism of the Cu2−xSe@N‐C cathode and the issues of volume expansion and oxidative dissolution related to the capacity degradation of the Cu2−xSe cathode. Furthermore, X‐ray absorption analysis and theoretical calculations reveal the presence of Se─C interactions between the ultrathin N‐doped carbon and Cu2−xSe. As a result, the physical and chemical dual‐protection of N‐doped carbon via Se‐C not only effectively stabilizes the structural evolution of Cu2−xSe but also endows it with faster electrode reaction kinetics.https://doi.org/10.1002/advs.202417084aqueous batteriesconversion‐type cathodescopper selenide
spellingShingle Fan Jiang
Haoyu Peng
Yiqian Wu
Yichen Li
Zeyu Zhang
Yue Wang
Jiuqiang Li
Jing Peng
Maolin Zhai
Tailoring the Structural Evolution of Multi‐Electron Redox Conversions via Strong Selenium–Carbon Interaction for Robust Aqueous Copper‐Ion Batteries
Advanced Science
aqueous batteries
conversion‐type cathodes
copper selenide
title Tailoring the Structural Evolution of Multi‐Electron Redox Conversions via Strong Selenium–Carbon Interaction for Robust Aqueous Copper‐Ion Batteries
title_full Tailoring the Structural Evolution of Multi‐Electron Redox Conversions via Strong Selenium–Carbon Interaction for Robust Aqueous Copper‐Ion Batteries
title_fullStr Tailoring the Structural Evolution of Multi‐Electron Redox Conversions via Strong Selenium–Carbon Interaction for Robust Aqueous Copper‐Ion Batteries
title_full_unstemmed Tailoring the Structural Evolution of Multi‐Electron Redox Conversions via Strong Selenium–Carbon Interaction for Robust Aqueous Copper‐Ion Batteries
title_short Tailoring the Structural Evolution of Multi‐Electron Redox Conversions via Strong Selenium–Carbon Interaction for Robust Aqueous Copper‐Ion Batteries
title_sort tailoring the structural evolution of multi electron redox conversions via strong selenium carbon interaction for robust aqueous copper ion batteries
topic aqueous batteries
conversion‐type cathodes
copper selenide
url https://doi.org/10.1002/advs.202417084
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