Coexistence of (O2)n- and Trapped Molecular O2 as the Oxidized Species in P2-Type Sodium 3d Layered Oxide and Stable Interface Enabled by Highly Fluorinated Electrolyte
The interface stability of cathode/electrolyte for Na-ion layered oxides is tightly related to the oxidized species formed during the electrochemical process. Herein, we for the first time decipher the coexistence of (O2)n- and trapped molecular O2 in the (de)sodiation process of P2-Na0.66[Li0.22Mn0.78]O2 by using advanced electron paramagnetic resonance (EPR) spectroscopy. An unstable interface of cathode/electrolyte can thus be envisaged with conventional carbonate electrolyte due to the high reactivity of the oxidized O species. We therefore introduce a highly fluorinated electrolyte to tentatively construct a stable and protective interface between P2-Na0.66[Li0.22Mn0.78]O2 and the electrolyte. As expected, an even and robust NaF-rich cathode-electrolyte interphase (CEI) film is formed in the highly fluorinated electrolyte, in sharp contrast to the nonuniform and friable organic-rich CEI formed in the conventional lowly fluorinated electrolyte. The in situ formed fluorinated CEI film can significantly mitigate the local structural degeneration of P2-Na0.66[Li0.22Mn0.78]O2 by refraining the irreversible Li/Mn dissolutions and O2 release, endowing a highly reversible oxygen redox reaction. Resultantly, P2-Na0.66[Li0.22Mn0.78]O2 in highly fluorinated electrolyte achieves a high Coulombic efficiency (CE) of >99% and an impressive cycling stability in the voltage range of 2.0-4.5 V (vs Na+/Na) under room temperature (147.6 mAh g-1, 100 cycles) and at 45 °C (142.5 mAh g-1, 100 cycles). This study highlights the profound impact of oxidized oxygen species on the interfacial stability of cathode/electrolyte and carves a new path for building stable interface and enabling highly stable oxygen redox reaction.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2021 |
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| Erschienen: |
2021 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:143 |
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| Enthalten in: |
Journal of the American Chemical Society - 143(2021), 44 vom: 10. Nov., Seite 18652-18664 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Zhao, Chong [VerfasserIn] |
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| Links: |
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| Anmerkungen: |
Date Revised 10.11.2021 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1021/jacs.1c08614 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM332397548 |
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| 100 | 1 | |a Zhao, Chong |e verfasserin |4 aut | |
| 245 | 1 | 0 | |a Coexistence of (O2)n- and Trapped Molecular O2 as the Oxidized Species in P2-Type Sodium 3d Layered Oxide and Stable Interface Enabled by Highly Fluorinated Electrolyte |
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| 500 | |a Date Revised 10.11.2021 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a The interface stability of cathode/electrolyte for Na-ion layered oxides is tightly related to the oxidized species formed during the electrochemical process. Herein, we for the first time decipher the coexistence of (O2)n- and trapped molecular O2 in the (de)sodiation process of P2-Na0.66[Li0.22Mn0.78]O2 by using advanced electron paramagnetic resonance (EPR) spectroscopy. An unstable interface of cathode/electrolyte can thus be envisaged with conventional carbonate electrolyte due to the high reactivity of the oxidized O species. We therefore introduce a highly fluorinated electrolyte to tentatively construct a stable and protective interface between P2-Na0.66[Li0.22Mn0.78]O2 and the electrolyte. As expected, an even and robust NaF-rich cathode-electrolyte interphase (CEI) film is formed in the highly fluorinated electrolyte, in sharp contrast to the nonuniform and friable organic-rich CEI formed in the conventional lowly fluorinated electrolyte. The in situ formed fluorinated CEI film can significantly mitigate the local structural degeneration of P2-Na0.66[Li0.22Mn0.78]O2 by refraining the irreversible Li/Mn dissolutions and O2 release, endowing a highly reversible oxygen redox reaction. Resultantly, P2-Na0.66[Li0.22Mn0.78]O2 in highly fluorinated electrolyte achieves a high Coulombic efficiency (CE) of >99% and an impressive cycling stability in the voltage range of 2.0-4.5 V (vs Na+/Na) under room temperature (147.6 mAh g-1, 100 cycles) and at 45 °C (142.5 mAh g-1, 100 cycles). This study highlights the profound impact of oxidized oxygen species on the interfacial stability of cathode/electrolyte and carves a new path for building stable interface and enabling highly stable oxygen redox reaction | ||
| 650 | 4 | |a Journal Article | |
| 700 | 1 | |a Li, Chao |e verfasserin |4 aut | |
| 700 | 1 | |a Liu, Hui |e verfasserin |4 aut | |
| 700 | 1 | |a Qiu, Qing |e verfasserin |4 aut | |
| 700 | 1 | |a Geng, Fushan |e verfasserin |4 aut | |
| 700 | 1 | |a Shen, Ming |e verfasserin |4 aut | |
| 700 | 1 | |a Tong, Wei |e verfasserin |4 aut | |
| 700 | 1 | |a Li, Jingxin |e verfasserin |4 aut | |
| 700 | 1 | |a Hu, Bingwen |e verfasserin |4 aut | |
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| 856 | 4 | 0 | |u http://dx.doi.org/10.1021/jacs.1c08614 |3 Volltext |
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