Structural Origins of Voltage Hysteresis in the Na-Ion Cathode P2-Na0.67[Mg0.28Mn0.72]O2 : A Combined Spectroscopic and Density Functional Theory Study
© 2021 The Authors. Published by American Chemical Society..
P2-layered sodium-ion battery (NIB) cathodes are a promising class of Na-ion electrode materials with high Na+ mobility and relatively high capacities. In this work, we report the structural changes that take place in P2-Na0.67[Mg0.28Mn0.72]O2. Using ex situ X-ray diffraction, Mn K-edge extended X-ray absorption fine structure, and 23Na NMR spectroscopy, we identify the bulk phase changes along the first electrochemical charge-discharge cycle-including the formation of a high-voltage "Z phase", an intergrowth of the OP4 and O2 phases. Our ab initio transition state searches reveal that reversible Mg2+ migration in the Z phase is both kinetically and thermodynamically favorable at high voltages. We propose that Mg2+ migration is a significant contributor to the observed voltage hysteresis in Na0.67[Mg0.28Mn0.72]O2 and identify qualitative changes in the Na+ ion mobility.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2021 |
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| Erschienen: |
2021 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:33 |
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| Enthalten in: |
Chemistry of materials : a publication of the American Chemical Society - 33(2021), 13 vom: 13. Juli, Seite 4890-4906 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Bassey, Euan N [VerfasserIn] |
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| Anmerkungen: |
Date Revised 02.04.2024 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1021/acs.chemmater.1c00248 |
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NLM328214914 |
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| 100 | 1 | |a Bassey, Euan N |e verfasserin |4 aut | |
| 245 | 1 | 0 | |a Structural Origins of Voltage Hysteresis in the Na-Ion Cathode P2-Na0.67[Mg0.28Mn0.72]O2 |b A Combined Spectroscopic and Density Functional Theory Study |
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| 500 | |a Date Revised 02.04.2024 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a © 2021 The Authors. Published by American Chemical Society. | ||
| 520 | |a P2-layered sodium-ion battery (NIB) cathodes are a promising class of Na-ion electrode materials with high Na+ mobility and relatively high capacities. In this work, we report the structural changes that take place in P2-Na0.67[Mg0.28Mn0.72]O2. Using ex situ X-ray diffraction, Mn K-edge extended X-ray absorption fine structure, and 23Na NMR spectroscopy, we identify the bulk phase changes along the first electrochemical charge-discharge cycle-including the formation of a high-voltage "Z phase", an intergrowth of the OP4 and O2 phases. Our ab initio transition state searches reveal that reversible Mg2+ migration in the Z phase is both kinetically and thermodynamically favorable at high voltages. We propose that Mg2+ migration is a significant contributor to the observed voltage hysteresis in Na0.67[Mg0.28Mn0.72]O2 and identify qualitative changes in the Na+ ion mobility | ||
| 650 | 4 | |a Journal Article | |
| 700 | 1 | |a Reeves, Philip J |e verfasserin |4 aut | |
| 700 | 1 | |a Jones, Michael A |e verfasserin |4 aut | |
| 700 | 1 | |a Lee, Jeongjae |e verfasserin |4 aut | |
| 700 | 1 | |a Seymour, Ieuan D |e verfasserin |4 aut | |
| 700 | 1 | |a Cibin, Giannantonio |e verfasserin |4 aut | |
| 700 | 1 | |a Grey, Clare P |e verfasserin |4 aut | |
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