Promoting the Reversible Oxygen Redox Reaction of Li‐Excess Layered Cathode Materials with Surface Vanadium Cation Doping
Abstract Li‐excess layered cathode (LLC) materials have a high theoretical specific capacity of 250 mAh g−1 induced by transition metal (cationic) and oxygen (anionic) redox activity. Especially, the oxygen redox reaction related to the activation of the Li2MnO3 domain plays the crucial role of prov...
| Main Authors: | , , , , , , |
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| Format: | Article |
| Language: | English |
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Wiley
2021-03-01
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| Series: | Advanced Science |
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| Online Access: | https://doi.org/10.1002/advs.202003013 |
| _version_ | 1818848344863145984 |
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| author | Yongju Lee Jaewook Shin Hyeonmuk Kang Daehee Lee Tae‐Hee Kim Young‐Kyun Kwon EunAe Cho |
| author_facet | Yongju Lee Jaewook Shin Hyeonmuk Kang Daehee Lee Tae‐Hee Kim Young‐Kyun Kwon EunAe Cho |
| author_sort | Yongju Lee |
| collection | DOAJ |
| description | Abstract Li‐excess layered cathode (LLC) materials have a high theoretical specific capacity of 250 mAh g−1 induced by transition metal (cationic) and oxygen (anionic) redox activity. Especially, the oxygen redox reaction related to the activation of the Li2MnO3 domain plays the crucial role of providing a high specific capacity. However, it also induces an irreversible oxygen release and accelerates the layered‐to‐spinel phase transformation and capacity fading. Here, it is shown that surface doping of vanadium (V5+) cations into LLC material suppresses both the irreversible oxygen release and undesirable phase transformation, resulting in the improvement of capacity retention. The V‐doped LLC shows a high discharge capacity of 244.3 ± 0.8 mAh g−1 with 92% retention after 100 cycles, whereas LLC delivers 233.6 ± 1.1 mAh g−1 with 74% retention. Furthermore, the average discharge voltage of V‐doped LLC drops by only 0.33 V after 100 cycles, while LLC exhibits 0.43 V of average discharge voltage drop. Experimental and theoretical investigations indicate that doped V‐doping increase the transition metal–oxygen (TMO) covalency and affect the oxidation state of peroxo‐like (O2)n− species during the delithiation process. The role of V‐doping to make the oxygen redox reversible in LLC materials for high‐energy density Li‐ion batteries is illustrated here. |
| first_indexed | 2024-12-19T06:15:51Z |
| format | Article |
| id | doaj.art-4689d157dd614f6e8b40aa92b91c541b |
| institution | Directory Open Access Journal |
| issn | 2198-3844 |
| language | English |
| last_indexed | 2024-12-19T06:15:51Z |
| publishDate | 2021-03-01 |
| publisher | Wiley |
| record_format | Article |
| series | Advanced Science |
| spelling | doaj.art-4689d157dd614f6e8b40aa92b91c541b2022-12-21T20:32:52ZengWileyAdvanced Science2198-38442021-03-0186n/an/a10.1002/advs.202003013Promoting the Reversible Oxygen Redox Reaction of Li‐Excess Layered Cathode Materials with Surface Vanadium Cation DopingYongju Lee0Jaewook Shin1Hyeonmuk Kang2Daehee Lee3Tae‐Hee Kim4Young‐Kyun Kwon5EunAe Cho6Department of Materials Science and Engineering Korea Advanced Institute of Science & Technology Daejeon 34141 KoreaDepartment of Materials Science and Engineering Korea Advanced Institute of Science & Technology Daejeon 34141 KoreaDepartment of Materials Science and Engineering Korea Advanced Institute of Science & Technology Daejeon 34141 KoreaDepartment of Materials Science and Engineering Korea Advanced Institute of Science & Technology Daejeon 34141 KoreaDepartment of Materials Science and Engineering Korea Advanced Institute of Science & Technology Daejeon 34141 KoreaDepartment of Physics and Research Institute of Basic Sciences Kyung Hee University Seoul 02447 KoreaDepartment of Materials Science and Engineering Korea Advanced Institute of Science & Technology Daejeon 34141 KoreaAbstract Li‐excess layered cathode (LLC) materials have a high theoretical specific capacity of 250 mAh g−1 induced by transition metal (cationic) and oxygen (anionic) redox activity. Especially, the oxygen redox reaction related to the activation of the Li2MnO3 domain plays the crucial role of providing a high specific capacity. However, it also induces an irreversible oxygen release and accelerates the layered‐to‐spinel phase transformation and capacity fading. Here, it is shown that surface doping of vanadium (V5+) cations into LLC material suppresses both the irreversible oxygen release and undesirable phase transformation, resulting in the improvement of capacity retention. The V‐doped LLC shows a high discharge capacity of 244.3 ± 0.8 mAh g−1 with 92% retention after 100 cycles, whereas LLC delivers 233.6 ± 1.1 mAh g−1 with 74% retention. Furthermore, the average discharge voltage of V‐doped LLC drops by only 0.33 V after 100 cycles, while LLC exhibits 0.43 V of average discharge voltage drop. Experimental and theoretical investigations indicate that doped V‐doping increase the transition metal–oxygen (TMO) covalency and affect the oxidation state of peroxo‐like (O2)n− species during the delithiation process. The role of V‐doping to make the oxygen redox reversible in LLC materials for high‐energy density Li‐ion batteries is illustrated here.https://doi.org/10.1002/advs.202003013cation dopingdensity functional theory calculationLi‐excess cathodelithium‐ion batteriesoxygen redox reaction |
| spellingShingle | Yongju Lee Jaewook Shin Hyeonmuk Kang Daehee Lee Tae‐Hee Kim Young‐Kyun Kwon EunAe Cho Promoting the Reversible Oxygen Redox Reaction of Li‐Excess Layered Cathode Materials with Surface Vanadium Cation Doping Advanced Science cation doping density functional theory calculation Li‐excess cathode lithium‐ion batteries oxygen redox reaction |
| title | Promoting the Reversible Oxygen Redox Reaction of Li‐Excess Layered Cathode Materials with Surface Vanadium Cation Doping |
| title_full | Promoting the Reversible Oxygen Redox Reaction of Li‐Excess Layered Cathode Materials with Surface Vanadium Cation Doping |
| title_fullStr | Promoting the Reversible Oxygen Redox Reaction of Li‐Excess Layered Cathode Materials with Surface Vanadium Cation Doping |
| title_full_unstemmed | Promoting the Reversible Oxygen Redox Reaction of Li‐Excess Layered Cathode Materials with Surface Vanadium Cation Doping |
| title_short | Promoting the Reversible Oxygen Redox Reaction of Li‐Excess Layered Cathode Materials with Surface Vanadium Cation Doping |
| title_sort | promoting the reversible oxygen redox reaction of li excess layered cathode materials with surface vanadium cation doping |
| topic | cation doping density functional theory calculation Li‐excess cathode lithium‐ion batteries oxygen redox reaction |
| url | https://doi.org/10.1002/advs.202003013 |
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