Enhanced oxygen redox reversibility and capacity retention of titanium-substituted Na4/7[□1/7Ti1/7Mn5/7]O2 in sodium-ion batteries

Stephanie Linnell; Eun Jeong Kim; Yong-Seok Choi; Moritz Hirsbrunner; Saki Imada; Atin Pramanik; Aida Fuente Cuesta; David Miller; Edoardo Fusco; Bela E Bode; John Irvine; Laurent Duda; David O. Scanlon; Anthony Robert Armstrong

doi:10.1039/D2TA01485H

Enhanced oxygen redox reversibility and capacity retention of titanium-substituted Na_4/7[□_1/7Ti_1/7Mn_5/7]O₂ in sodium-ion batteries

Stephanie Linnell, Eun Jeong Kim, Yong-Seok Choi, Moritz Hirsbrunner, Saki Imada, Atin Pramanik, Aida Fuente Cuesta, David Miller, Edoardo Fusco, Bela E Bode, John Irvine, Laurent Duda, David O. Scanlon, Anthony Robert Armstrong^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

Abstract

Anion redox reactions offer a means of enhancing the capacity of layered sodium transition metal oxide positive electrode materials. However, oxygen redox reactions typically show limited reversibility and irreversible structural changes upon cycling, resulting in rapid capacity loss. Here, the Ti substituted Na_4/7[□_1/7Ti_1/7Mn_5/7]O₂ (where □ represents a transition metal vacancy) is presented as a positive electrode material for sodium ion batteries. Na_4/7[□_1/7Ti_1/7Mn_5/7]O₂ delivers a reversible capacity of 167 mAh g ^-1 after 25 cycles at 10 mA g ^-1 within the voltage range of 1.6 – 4.4 V and presents enhanced stability compared with Na_4/7[□_1/7Mn_6/7]O₂ over the voltage range 3.0 – 4.4 V. The structural and electronic structural changes of this Ti⁴⁺ substituted phase are investigated by powder X-ray diffraction, X ray absorption spectroscopy, electron paramagnetic resonance and Raman spectroscopy, supported by density functional theory calculations. These results show that the Na_4/7[□_1/7Mn_6/7]O₂ structure is maintained between 3.0 – 4.4 V, and the presence of TiO₆ octahedra in Na_4/7[□_1/7Ti_1/7Mn_5/7]O₂ relieves structural distortions from Jahn Teller distorted Mn³⁺O₆ between 1.6 – 4.4 V. Furthermore, Ti⁴⁺ substitution stabilises the adjacent O 2p orbitals and raises the ionicity of the Mn O bonds, increasing the operating potential of Na_4/7[□_1/7Ti_1/7Mn_5/7]O₂. Thereby providing evidence that the improved electrochemical performance of Na4/7[□1/7Ti1/7Mn5/7]O2 can be attributed to Ti4+ substitution. This work provides insight and strategies for improving the structural stability and electrochemical performance of sodium layered oxides.

Original language	English
Pages (from-to)	9941-9953
Journal	Journal of Materials Chemistry A
Volume	10
Issue number	18
Early online date	30 Mar 2022
DOIs	https://doi.org/10.1039/D2TA01485H
Publication status	Published - 14 May 2022

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Linnell_2022_JMCA_EnhancedOxygen_CC
Copyright 2022 The Author(s). Open Access. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
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Light Element Analysis Facility (LEAF): Light Element Analysis Facility (LEAF)
Irvine, J. T. S. (PI), Baker, R. (CoI) & Miller, D. N. (CoI)
EPSRC
5/04/20 → 4/04/23
Project: Standard

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Linnell, S., Kim, E. J., Choi, Y.-S., Hirsbrunner, M., Imada, S., Pramanik, A., Fuente Cuesta, A., Miller, D., Fusco, E., Bode, B. E., Irvine, J., Duda, L., Scanlon, D. O., & Armstrong, A. R. (2022). Enhanced oxygen redox reversibility and capacity retention of titanium-substituted Na_4/7[□_1/7Ti_1/7Mn_5/7]O₂ in sodium-ion batteries. Journal of Materials Chemistry A, 10(18), 9941-9953. https://doi.org/10.1039/D2TA01485H

@article{ababa6aa56aa4632947910b134e4802c,

title = "Enhanced oxygen redox reversibility and capacity retention of titanium-substituted Na4/7[□1/7Ti1/7Mn5/7]O2 in sodium-ion batteries",

abstract = "Anion redox reactions offer a means of enhancing the capacity of layered sodium transition metal oxide positive electrode materials. However, oxygen redox reactions typically show limited reversibility and irreversible structural changes upon cycling, resulting in rapid capacity loss. Here, the Ti substituted Na4/7[□1/7Ti1/7Mn5/7]O2 (where □ represents a transition metal vacancy) is presented as a positive electrode material for sodium ion batteries. Na4/7[□1/7Ti1/7Mn5/7]O2 delivers a reversible capacity of 167 mAh g -1 after 25 cycles at 10 mA g -1 within the voltage range of 1.6 – 4.4 V and presents enhanced stability compared with Na4/7[□1/7Mn6/7]O2 over the voltage range 3.0 – 4.4 V. The structural and electronic structural changes of this Ti4+ substituted phase are investigated by powder X-ray diffraction, X ray absorption spectroscopy, electron paramagnetic resonance and Raman spectroscopy, supported by density functional theory calculations. These results show that the Na4/7[□1/7Mn6/7]O2 structure is maintained between 3.0 – 4.4 V, and the presence of TiO6 octahedra in Na4/7[□1/7Ti1/7Mn5/7]O2 relieves structural distortions from Jahn Teller distorted Mn3+O6 between 1.6 – 4.4 V. Furthermore, Ti4+ substitution stabilises the adjacent O 2p orbitals and raises the ionicity of the Mn O bonds, increasing the operating potential of Na4/7[□1/7Ti1/7Mn5/7]O2. Thereby providing evidence that the improved electrochemical performance of Na4/7[□1/7Ti1/7Mn5/7]O2 can be attributed to Ti4+ substitution. This work provides insight and strategies for improving the structural stability and electrochemical performance of sodium layered oxides.",

author = "Stephanie Linnell and Kim, {Eun Jeong} and Yong-Seok Choi and Moritz Hirsbrunner and Saki Imada and Atin Pramanik and {Fuente Cuesta}, Aida and David Miller and Edoardo Fusco and Bode, {Bela E} and John Irvine and Laurent Duda and Scanlon, {David O.} and Armstrong, {Anthony Robert}",

note = "L. D. gratefully acknowledges financial support from the Swedish Energy Agency (contract 2020-005246). Y.C. and D.O.S. are grateful to the Faraday Institution for funding the MICHAEL computing cluster hosted at University College London (UCL). Our membership of the UKs HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202, EP/R029431), this work used the ARCHER2 UK National Supercomputing Service(http://www.archer2.ac.uk). We are also grateful to the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/P020194/1 and EP/T022213/1). We are grateful to the Engineering and Physical Sciences Research Council (EPSRC) Light Element Facility Grant (EP/T019298/1) for funding the acquisition of the Raman spectrometer. EF is grateful for an EaStCHEM studentship. This work was supported by the Faraday Institution (grant number FIRG018).",

year = "2022",

month = may,

day = "14",

doi = "10.1039/D2TA01485H",

language = "English",

volume = "10",

pages = "9941--9953",

journal = "Journal of Materials Chemistry A",

issn = "2050-7488",

publisher = "ROYAL SOC CHEMISTRY",

number = "18",

}

Linnell, S, Kim, EJ, Choi, Y-S, Hirsbrunner, M, Imada, S, Pramanik, A, Fuente Cuesta, A, Miller, D, Fusco, E, Bode, BE , Irvine, J, Duda, L, Scanlon, DO & Armstrong, AR 2022, 'Enhanced oxygen redox reversibility and capacity retention of titanium-substituted Na_4/7[□_1/7Ti_1/7Mn_5/7]O₂ in sodium-ion batteries', Journal of Materials Chemistry A, vol. 10, no. 18, pp. 9941-9953. https://doi.org/10.1039/D2TA01485H

TY - JOUR

T1 - Enhanced oxygen redox reversibility and capacity retention of titanium-substituted Na4/7[□1/7Ti1/7Mn5/7]O2 in sodium-ion batteries

AU - Linnell, Stephanie

AU - Kim, Eun Jeong

AU - Choi, Yong-Seok

AU - Hirsbrunner, Moritz

AU - Imada, Saki

AU - Pramanik, Atin

AU - Fuente Cuesta, Aida

AU - Miller, David

AU - Fusco, Edoardo

AU - Bode, Bela E

AU - Irvine, John

AU - Duda, Laurent

AU - Scanlon, David O.

AU - Armstrong, Anthony Robert

N1 - L. D. gratefully acknowledges financial support from the Swedish Energy Agency (contract 2020-005246). Y.C. and D.O.S. are grateful to the Faraday Institution for funding the MICHAEL computing cluster hosted at University College London (UCL). Our membership of the UKs HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202, EP/R029431), this work used the ARCHER2 UK National Supercomputing Service(http://www.archer2.ac.uk). We are also grateful to the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/P020194/1 and EP/T022213/1). We are grateful to the Engineering and Physical Sciences Research Council (EPSRC) Light Element Facility Grant (EP/T019298/1) for funding the acquisition of the Raman spectrometer. EF is grateful for an EaStCHEM studentship. This work was supported by the Faraday Institution (grant number FIRG018).

PY - 2022/5/14

Y1 - 2022/5/14

N2 - Anion redox reactions offer a means of enhancing the capacity of layered sodium transition metal oxide positive electrode materials. However, oxygen redox reactions typically show limited reversibility and irreversible structural changes upon cycling, resulting in rapid capacity loss. Here, the Ti substituted Na4/7[□1/7Ti1/7Mn5/7]O2 (where □ represents a transition metal vacancy) is presented as a positive electrode material for sodium ion batteries. Na4/7[□1/7Ti1/7Mn5/7]O2 delivers a reversible capacity of 167 mAh g -1 after 25 cycles at 10 mA g -1 within the voltage range of 1.6 – 4.4 V and presents enhanced stability compared with Na4/7[□1/7Mn6/7]O2 over the voltage range 3.0 – 4.4 V. The structural and electronic structural changes of this Ti4+ substituted phase are investigated by powder X-ray diffraction, X ray absorption spectroscopy, electron paramagnetic resonance and Raman spectroscopy, supported by density functional theory calculations. These results show that the Na4/7[□1/7Mn6/7]O2 structure is maintained between 3.0 – 4.4 V, and the presence of TiO6 octahedra in Na4/7[□1/7Ti1/7Mn5/7]O2 relieves structural distortions from Jahn Teller distorted Mn3+O6 between 1.6 – 4.4 V. Furthermore, Ti4+ substitution stabilises the adjacent O 2p orbitals and raises the ionicity of the Mn O bonds, increasing the operating potential of Na4/7[□1/7Ti1/7Mn5/7]O2. Thereby providing evidence that the improved electrochemical performance of Na4/7[□1/7Ti1/7Mn5/7]O2 can be attributed to Ti4+ substitution. This work provides insight and strategies for improving the structural stability and electrochemical performance of sodium layered oxides.

AB - Anion redox reactions offer a means of enhancing the capacity of layered sodium transition metal oxide positive electrode materials. However, oxygen redox reactions typically show limited reversibility and irreversible structural changes upon cycling, resulting in rapid capacity loss. Here, the Ti substituted Na4/7[□1/7Ti1/7Mn5/7]O2 (where □ represents a transition metal vacancy) is presented as a positive electrode material for sodium ion batteries. Na4/7[□1/7Ti1/7Mn5/7]O2 delivers a reversible capacity of 167 mAh g -1 after 25 cycles at 10 mA g -1 within the voltage range of 1.6 – 4.4 V and presents enhanced stability compared with Na4/7[□1/7Mn6/7]O2 over the voltage range 3.0 – 4.4 V. The structural and electronic structural changes of this Ti4+ substituted phase are investigated by powder X-ray diffraction, X ray absorption spectroscopy, electron paramagnetic resonance and Raman spectroscopy, supported by density functional theory calculations. These results show that the Na4/7[□1/7Mn6/7]O2 structure is maintained between 3.0 – 4.4 V, and the presence of TiO6 octahedra in Na4/7[□1/7Ti1/7Mn5/7]O2 relieves structural distortions from Jahn Teller distorted Mn3+O6 between 1.6 – 4.4 V. Furthermore, Ti4+ substitution stabilises the adjacent O 2p orbitals and raises the ionicity of the Mn O bonds, increasing the operating potential of Na4/7[□1/7Ti1/7Mn5/7]O2. Thereby providing evidence that the improved electrochemical performance of Na4/7[□1/7Ti1/7Mn5/7]O2 can be attributed to Ti4+ substitution. This work provides insight and strategies for improving the structural stability and electrochemical performance of sodium layered oxides.

U2 - 10.1039/D2TA01485H

DO - 10.1039/D2TA01485H

M3 - Article

SN - 2050-7488

VL - 10

SP - 9941

EP - 9953

JO - Journal of Materials Chemistry A

JF - Journal of Materials Chemistry A

IS - 18

ER -

Enhanced oxygen redox reversibility and capacity retention of titanium-substituted Na4/7[□1/7Ti1/7Mn5/7]O2 in sodium-ion batteries

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Enhanced oxygen redox reversibility and capacity retention of titanium-substituted Na_4/7[□_1/7Ti_1/7Mn_5/7]O₂ in sodium-ion batteries