Improved cycling stability in high-capacity Li-rich vanadium containing disordered rock salt oxyfluoride cathodes

Christian Baur*, Ida Källquist, Johann Chable, Jin Hyun Chang, Rune E. Johnsen, Francisco Ruiz-Zepeda, Jean-Marcel Ateba Mba, Andrew J. Naylor, Juan Maria García-Lastra, Tejs Vegge, Franziska Klein, Annika R. Schür, Poul Norby, Kristina Edström, Maria Hahlin, Maximilian Fichtner

*Corresponding author for this work

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Abstract

Lithium-rich transition metal disordered rock salt (DRS) oxyfluorides have the potential to lessen one large bottleneck for lithium ion batteries by improving the cathode capacity. However, irreversible reactions at the electrode/electrolyte interface have so far led to fast capacity fading during electrochemical cycling. Here, we report the synthesis of two new Li-rich transition metal oxyfluorides Li2V0.5Ti0.5O2F and Li2V0.5Fe0.5O2F using the mechanochemical ball milling procedure. Both materials show substantially improved cycling stability compared to Li2VO2F. Rietveld refinements of synchrotron X-ray diffraction patterns reveal the DRS structure of the materials. Based on density functional theory (DFT) calculations, we demonstrate that substitution of V3+ with Ti3+ and Fe3+ favors disordering of the mixed metastable DRS oxyfluoride phase. Hard X-ray photoelectron spectroscopy shows that the substitution stabilizes the active material electrode particle surface and increases the reversibility of the V3+/V5+ redox couple. This work presents a strategy for stabilization of the DRS structure leading to improved electrochemical cyclability of the materials.
Original languageEnglish
JournalJournal of Materials Chemistry A
Volume7
Issue number37
Pages (from-to)21244-21253
ISSN2050-7488
DOIs
Publication statusPublished - 2019

Cite this

Baur, Christian ; Källquist, Ida ; Chable, Johann ; Chang, Jin Hyun ; Johnsen, Rune E. ; Ruiz-Zepeda, Francisco ; Ateba Mba, Jean-Marcel ; Naylor, Andrew J. ; García-Lastra, Juan Maria ; Vegge, Tejs ; Klein, Franziska ; Schür, Annika R. ; Norby, Poul ; Edström, Kristina ; Hahlin, Maria ; Fichtner, Maximilian . / Improved cycling stability in high-capacity Li-rich vanadium containing disordered rock salt oxyfluoride cathodes. In: Journal of Materials Chemistry A. 2019 ; Vol. 7, No. 37. pp. 21244-21253.
@article{c6dda492a255497f98da216f329c1635,
title = "Improved cycling stability in high-capacity Li-rich vanadium containing disordered rock salt oxyfluoride cathodes",
abstract = "Lithium-rich transition metal disordered rock salt (DRS) oxyfluorides have the potential to lessen one large bottleneck for lithium ion batteries by improving the cathode capacity. However, irreversible reactions at the electrode/electrolyte interface have so far led to fast capacity fading during electrochemical cycling. Here, we report the synthesis of two new Li-rich transition metal oxyfluorides Li2V0.5Ti0.5O2F and Li2V0.5Fe0.5O2F using the mechanochemical ball milling procedure. Both materials show substantially improved cycling stability compared to Li2VO2F. Rietveld refinements of synchrotron X-ray diffraction patterns reveal the DRS structure of the materials. Based on density functional theory (DFT) calculations, we demonstrate that substitution of V3+ with Ti3+ and Fe3+ favors disordering of the mixed metastable DRS oxyfluoride phase. Hard X-ray photoelectron spectroscopy shows that the substitution stabilizes the active material electrode particle surface and increases the reversibility of the V3+/V5+ redox couple. This work presents a strategy for stabilization of the DRS structure leading to improved electrochemical cyclability of the materials.",
author = "Christian Baur and Ida K{\"a}llquist and Johann Chable and Chang, {Jin Hyun} and Johnsen, {Rune E.} and Francisco Ruiz-Zepeda and {Ateba Mba}, Jean-Marcel and Naylor, {Andrew J.} and Garc{\'i}a-Lastra, {Juan Maria} and Tejs Vegge and Franziska Klein and Sch{\"u}r, {Annika R.} and Poul Norby and Kristina Edstr{\"o}m and Maria Hahlin and Maximilian Fichtner",
year = "2019",
doi = "10.1039/c9ta06291b",
language = "English",
volume = "7",
pages = "21244--21253",
journal = "Journal of Materials Chemistry A",
issn = "2050-7488",
publisher = "RSC Publications",
number = "37",

}

Baur, C, Källquist, I, Chable, J, Chang, JH, Johnsen, RE, Ruiz-Zepeda, F, Ateba Mba, J-M, Naylor, AJ, García-Lastra, JM, Vegge, T, Klein, F, Schür, AR, Norby, P, Edström, K, Hahlin, M & Fichtner, M 2019, 'Improved cycling stability in high-capacity Li-rich vanadium containing disordered rock salt oxyfluoride cathodes', Journal of Materials Chemistry A, vol. 7, no. 37, pp. 21244-21253. https://doi.org/10.1039/c9ta06291b

Improved cycling stability in high-capacity Li-rich vanadium containing disordered rock salt oxyfluoride cathodes. / Baur, Christian ; Källquist, Ida; Chable, Johann ; Chang, Jin Hyun; Johnsen, Rune E.; Ruiz-Zepeda, Francisco ; Ateba Mba, Jean-Marcel ; Naylor, Andrew J. ; García-Lastra, Juan Maria; Vegge, Tejs; Klein, Franziska ; Schür, Annika R.; Norby, Poul; Edström, Kristina; Hahlin, Maria ; Fichtner, Maximilian .

In: Journal of Materials Chemistry A, Vol. 7, No. 37, 2019, p. 21244-21253.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - Improved cycling stability in high-capacity Li-rich vanadium containing disordered rock salt oxyfluoride cathodes

AU - Baur, Christian

AU - Källquist, Ida

AU - Chable, Johann

AU - Chang, Jin Hyun

AU - Johnsen, Rune E.

AU - Ruiz-Zepeda, Francisco

AU - Ateba Mba, Jean-Marcel

AU - Naylor, Andrew J.

AU - García-Lastra, Juan Maria

AU - Vegge, Tejs

AU - Klein, Franziska

AU - Schür, Annika R.

AU - Norby, Poul

AU - Edström, Kristina

AU - Hahlin, Maria

AU - Fichtner, Maximilian

PY - 2019

Y1 - 2019

N2 - Lithium-rich transition metal disordered rock salt (DRS) oxyfluorides have the potential to lessen one large bottleneck for lithium ion batteries by improving the cathode capacity. However, irreversible reactions at the electrode/electrolyte interface have so far led to fast capacity fading during electrochemical cycling. Here, we report the synthesis of two new Li-rich transition metal oxyfluorides Li2V0.5Ti0.5O2F and Li2V0.5Fe0.5O2F using the mechanochemical ball milling procedure. Both materials show substantially improved cycling stability compared to Li2VO2F. Rietveld refinements of synchrotron X-ray diffraction patterns reveal the DRS structure of the materials. Based on density functional theory (DFT) calculations, we demonstrate that substitution of V3+ with Ti3+ and Fe3+ favors disordering of the mixed metastable DRS oxyfluoride phase. Hard X-ray photoelectron spectroscopy shows that the substitution stabilizes the active material electrode particle surface and increases the reversibility of the V3+/V5+ redox couple. This work presents a strategy for stabilization of the DRS structure leading to improved electrochemical cyclability of the materials.

AB - Lithium-rich transition metal disordered rock salt (DRS) oxyfluorides have the potential to lessen one large bottleneck for lithium ion batteries by improving the cathode capacity. However, irreversible reactions at the electrode/electrolyte interface have so far led to fast capacity fading during electrochemical cycling. Here, we report the synthesis of two new Li-rich transition metal oxyfluorides Li2V0.5Ti0.5O2F and Li2V0.5Fe0.5O2F using the mechanochemical ball milling procedure. Both materials show substantially improved cycling stability compared to Li2VO2F. Rietveld refinements of synchrotron X-ray diffraction patterns reveal the DRS structure of the materials. Based on density functional theory (DFT) calculations, we demonstrate that substitution of V3+ with Ti3+ and Fe3+ favors disordering of the mixed metastable DRS oxyfluoride phase. Hard X-ray photoelectron spectroscopy shows that the substitution stabilizes the active material electrode particle surface and increases the reversibility of the V3+/V5+ redox couple. This work presents a strategy for stabilization of the DRS structure leading to improved electrochemical cyclability of the materials.

U2 - 10.1039/c9ta06291b

DO - 10.1039/c9ta06291b

M3 - Journal article

VL - 7

SP - 21244

EP - 21253

JO - Journal of Materials Chemistry A

JF - Journal of Materials Chemistry A

SN - 2050-7488

IS - 37

ER -