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Guest Ion‐Dependent Reaction Mechanisms of New Pseudocapacitive Mg₃V₄(PO₄)₆/Carbon Composite as Negative Electrode for Monovalent‐Ion Batteries

Fu, Qiang ; Schwarz, Björn ; Ding, Ziming ; Sarapulova, Angelina ; Weidler, Peter G. ; Missyul, Alexander ; Etter, Martin ; Welter, Edmund ; Hua, Weibo ; Knapp, Michael ; Dsoke, Sonia ; Ehrenberg, Helmut (2023)
Guest Ion‐Dependent Reaction Mechanisms of New Pseudocapacitive Mg₃V₄(PO₄)₆/Carbon Composite as Negative Electrode for Monovalent‐Ion Batteries.
In: Advanced Science, 2023, 10 (11)
doi: 10.26083/tuprints-00023742
Artikel, Zweitveröffentlichung, Verlagsversion

Kurzbeschreibung (Abstract)

Polyanion‐type phosphate materials, such as M₃V₂(PO₄)₃ (M = Li/Na/K), are promising as insertion‐type negative electrodes for monovalent‐ion batteries including Li/Na/K‐ion batteries (lithium‐ion batteries (LIBs), sodium‐ion batteries (SIBs), and potassium‐ion batteries (PIBs)) with fast charging/discharging and distinct redox peaks. However, it remains a great challenge to understand the reaction mechanism of materials upon monovalent‐ion insertion. Here, triclinic Mg₃V₄(PO₄)₆/carbon composite (MgVP/C) with high thermal stability is synthesized via ball‐milling and carbon‐thermal reduction method and applied as a pseudocapacitive negative electrode in LIBs, SIBs, and PIBs. In operando and ex situ studies demonstrate the guest ion‐dependent reaction mechanisms of MgVP/C upon monovalent‐ion storage due to different sizes. MgVP/C undergoes an indirect conversion reaction to form Mg⁰, V⁰, and Li₃PO₄ in LIBs, while in SIBs/PIBs the material only experiences a solid solution with the reduction of V³⁺ to V²⁺. Moreover, in LIBs, MgVP/C delivers initial lithiation/delithiation capacities of 961/607 mAh g⁻¹ (30/19 Li⁺ ions) for the first cycle, despite its low initial Coulombic efficiency, fast capacity decay for the first 200 cycles, and limited reversible insertion/deinsertion of 2 Na⁺/K⁺ ions in SIBs/PIBs. This work reveals a new pseudocapacitive material and provides an advanced understanding of polyanion phosphate negative material for monovalent‐ion batteries with guest ion‐dependent energy storage mechanisms.

Typ des Eintrags: Artikel
Erschienen: 2023
Autor(en): Fu, Qiang ; Schwarz, Björn ; Ding, Ziming ; Sarapulova, Angelina ; Weidler, Peter G. ; Missyul, Alexander ; Etter, Martin ; Welter, Edmund ; Hua, Weibo ; Knapp, Michael ; Dsoke, Sonia ; Ehrenberg, Helmut
Art des Eintrags: Zweitveröffentlichung
Titel: Guest Ion‐Dependent Reaction Mechanisms of New Pseudocapacitive Mg₃V₄(PO₄)₆/Carbon Composite as Negative Electrode for Monovalent‐Ion Batteries
Sprache: Englisch
Publikationsjahr: 2023
Ort: Darmstadt
Publikationsdatum der Erstveröffentlichung: 2023
Verlag: Wiley-VCH
Titel der Zeitschrift, Zeitung oder Schriftenreihe: Advanced Science
Jahrgang/Volume einer Zeitschrift: 10
(Heft-)Nummer: 11
Kollation: 12 Seiten
DOI: 10.26083/tuprints-00023742
URL / URN: https://tuprints.ulb.tu-darmstadt.de/23742
Zugehörige Links:
Herkunft: Zweitveröffentlichung DeepGreen
Kurzbeschreibung (Abstract):

Polyanion‐type phosphate materials, such as M₃V₂(PO₄)₃ (M = Li/Na/K), are promising as insertion‐type negative electrodes for monovalent‐ion batteries including Li/Na/K‐ion batteries (lithium‐ion batteries (LIBs), sodium‐ion batteries (SIBs), and potassium‐ion batteries (PIBs)) with fast charging/discharging and distinct redox peaks. However, it remains a great challenge to understand the reaction mechanism of materials upon monovalent‐ion insertion. Here, triclinic Mg₃V₄(PO₄)₆/carbon composite (MgVP/C) with high thermal stability is synthesized via ball‐milling and carbon‐thermal reduction method and applied as a pseudocapacitive negative electrode in LIBs, SIBs, and PIBs. In operando and ex situ studies demonstrate the guest ion‐dependent reaction mechanisms of MgVP/C upon monovalent‐ion storage due to different sizes. MgVP/C undergoes an indirect conversion reaction to form Mg⁰, V⁰, and Li₃PO₄ in LIBs, while in SIBs/PIBs the material only experiences a solid solution with the reduction of V³⁺ to V²⁺. Moreover, in LIBs, MgVP/C delivers initial lithiation/delithiation capacities of 961/607 mAh g⁻¹ (30/19 Li⁺ ions) for the first cycle, despite its low initial Coulombic efficiency, fast capacity decay for the first 200 cycles, and limited reversible insertion/deinsertion of 2 Na⁺/K⁺ ions in SIBs/PIBs. This work reveals a new pseudocapacitive material and provides an advanced understanding of polyanion phosphate negative material for monovalent‐ion batteries with guest ion‐dependent energy storage mechanisms.

Freie Schlagworte: in operando synchrotron diffraction, in operando X‐ray absorption spectroscopy, magnetic properties, monovalent‐ion batteries, triclinic Mg₃V₄(PO₄)₆
Status: Verlagsversion
URN: urn:nbn:de:tuda-tuprints-237429
Sachgruppe der Dewey Dezimalklassifikatin (DDC): 600 Technik, Medizin, angewandte Wissenschaften > 660 Technische Chemie
Fachbereich(e)/-gebiet(e): 11 Fachbereich Material- und Geowissenschaften
11 Fachbereich Material- und Geowissenschaften > Materialwissenschaft
11 Fachbereich Material- und Geowissenschaften > Materialwissenschaft > In-Situ Elektronenmikroskopie
Hinterlegungsdatum: 28 Apr 2023 12:42
Letzte Änderung: 02 Mai 2023 06:20
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