Largely Pseudocapacitive Two-Dimensional Conjugated Metal-Organic Framework Anodes with Lowest Unoccupied Molecular Orbital Localized in Nickel-bis(dithiolene) Linkages
Although two-dimensional conjugated metal-organic frameworks (2D c-MOFs) provide an ideal platform for precise tailoring of capacitive electrode materials, high-capacitance 2D c-MOFs for non-aqueous supercapacitors remain to be further explored. Herein, we report a novel phthalocyanine-based nickel-bis(dithiolene) (NiS4)-linked 2D c-MOF (denoted as Ni2[CuPcS8]) with outstanding pseudocapacitive properties in 1 M TEABF4/acetonitrile. Each NiS4 linkage is disclosed to reversibly accommodate two electrons, conferring the Ni2[CuPcS8] electrode a two-step Faradic reaction with a record-high specific capacitance among the reported 2D c-MOFs in non-aqueous electrolytes (312 F g-1) and remarkable cycling stability (93.5% after 10,000 cycles). Multiple analyses unveil that the unique electron-storage capability of Ni2[CuPcS8] originates from its localized lowest unoccupied molecular orbital (LUMO) over the nickel-bis(dithiolene) linkage, which allows the efficient delocalization of the injected electrons throughout the conjugated linkage units without inducing apparent bonding stress. The Ni2[CuPcS8] anode is used to demonstrate an asymmetric supercapacitor device that delivers a high operating voltage of 2.3 V, a maximum energy density of 57.4 Wh kg-1, and ultralong stability over 5000 cycles.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2023 |
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| Erschienen: |
2023 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:145 |
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| Enthalten in: |
Journal of the American Chemical Society - 145(2023), 11 vom: 22. März, Seite 6247-6256 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Zhang, Panpan [VerfasserIn] |
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| Anmerkungen: |
Date Completed 22.03.2023 Date Revised 22.03.2023 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1021/jacs.2c12684 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM35399197X |
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| 245 | 1 | 0 | |a Largely Pseudocapacitive Two-Dimensional Conjugated Metal-Organic Framework Anodes with Lowest Unoccupied Molecular Orbital Localized in Nickel-bis(dithiolene) Linkages |
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| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a Although two-dimensional conjugated metal-organic frameworks (2D c-MOFs) provide an ideal platform for precise tailoring of capacitive electrode materials, high-capacitance 2D c-MOFs for non-aqueous supercapacitors remain to be further explored. Herein, we report a novel phthalocyanine-based nickel-bis(dithiolene) (NiS4)-linked 2D c-MOF (denoted as Ni2[CuPcS8]) with outstanding pseudocapacitive properties in 1 M TEABF4/acetonitrile. Each NiS4 linkage is disclosed to reversibly accommodate two electrons, conferring the Ni2[CuPcS8] electrode a two-step Faradic reaction with a record-high specific capacitance among the reported 2D c-MOFs in non-aqueous electrolytes (312 F g-1) and remarkable cycling stability (93.5% after 10,000 cycles). Multiple analyses unveil that the unique electron-storage capability of Ni2[CuPcS8] originates from its localized lowest unoccupied molecular orbital (LUMO) over the nickel-bis(dithiolene) linkage, which allows the efficient delocalization of the injected electrons throughout the conjugated linkage units without inducing apparent bonding stress. The Ni2[CuPcS8] anode is used to demonstrate an asymmetric supercapacitor device that delivers a high operating voltage of 2.3 V, a maximum energy density of 57.4 Wh kg-1, and ultralong stability over 5000 cycles | ||
| 650 | 4 | |a Journal Article | |
| 700 | 1 | |a Wang, Mingchao |e verfasserin |4 aut | |
| 700 | 1 | |a Liu, Yannan |e verfasserin |4 aut | |
| 700 | 1 | |a Fu, Yubin |e verfasserin |4 aut | |
| 700 | 1 | |a Gao, Mingming |e verfasserin |4 aut | |
| 700 | 1 | |a Wang, Gang |e verfasserin |4 aut | |
| 700 | 1 | |a Wang, Faxing |e verfasserin |4 aut | |
| 700 | 1 | |a Wang, Zhiyong |e verfasserin |4 aut | |
| 700 | 1 | |a Chen, Guangbo |e verfasserin |4 aut | |
| 700 | 1 | |a Yang, Sheng |e verfasserin |4 aut | |
| 700 | 1 | |a Liu, Youwen |e verfasserin |4 aut | |
| 700 | 1 | |a Dong, Renhao |e verfasserin |4 aut | |
| 700 | 1 | |a Yu, Minghao |e verfasserin |4 aut | |
| 700 | 1 | |a Lu, Xing |e verfasserin |4 aut | |
| 700 | 1 | |a Feng, Xinliang |e verfasserin |4 aut | |
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