Na2.4Al0.4Mn2.6O7 anionic redox cathode material for sodium-ion batteries – a combined experimental and theoretical approach to elucidate its charge storage mechanism

Cindy Soares; Begoña Silván; Yong-Seok Choi; Veronica Celorrio; Valerie R. Seymour; Giannantonio Cibin; John M. Griffin; David O. Scanlon; Nuria Tapia-Ruiz

doi:10.1039/D1TA05137G

Na_2.4Al_0.4Mn_2.6O₇ anionic redox cathode material for sodium-ion batteries – a combined experimental and theoretical approach to elucidate its charge storage mechanism

Cindy Soares, Begoña Silván, Yong-Seok Choi, Veronica Celorrio, Valerie R. Seymour, Giannantonio Cibin, John M. Griffin, David O. Scanlon, Nuria Tapia-Ruiz^*

^*Corresponding author for this work

Chemistry

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

24 Downloads (Pure)

Abstract

Here we report the synthesis via ceramic methods of the high-performance Mn-rich Na_2.4Al_0.4Mn_2.6O₇ oxygen-redox cathode material for Na-ion batteries, which we use as a testbed material to study the effects of Al substitution and subsequent Na excess in the high-capacity, anionic redox-based cathode material, Na₂Mn₃O₇. The material shows a stable electrochemical performance, with a specific capacity of 215 mA h g⁻¹ in the 1.5–4.7 V voltage range at C/20 and a capacity retention of 90% after 40 cycles. Using a combination of electrochemical and structural analysis together with hybrid density functional theory calculations we explain the behaviour of this material with changes in Mn/anionic redox reactions and associated O₂ release reactions occurring during electrochemical cycling (Na⁺ ion insertion/extraction), and compare these findings to Na₂Mn₃O₇. We expect that these results will advance understanding of the effect of dopants in Mn-rich cathode materials with oxygen redox activity to pave their way towards high-performance sodium-ion batteries.

Original language	English
Pages (from-to)	7341-7356
Number of pages	16
Journal	Journal of Materials Chemistry A
Volume	10
Issue number	13
Early online date	16 Dec 2021
DOIs	https://doi.org/10.1039/D1TA05137G
Publication status	Published - 7 Apr 2022

Bibliographical note

Acknowledgments:
NTR would like to thank Lancaster University, the Royal Society (RG170150) and the Faraday Institution (FIRG018) for financial support. We acknowledge the Science and Technology Facilities Council (STFC) for access to B18 beamtime at the Diamond Light Source (SP21847). YC and DOS are grateful to the Faraday Institution for funding the MICHAEL computing cluster hosted at University College London (UCL). The calculations have been also carried out on the Myriad (Myriad@UCL), Young (Young@UCL), and Kathleen (Kathleen@UCL) High Performance Computing Facility provisioned by UCL. Via our membership of the UKs HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202, EP/R029431), this work used the ARCHER UK National Supercomputing Service (http://www.archer.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).

Access to Document

10.1039/D1TA05137GLicence: Creative Commons: Attribution (CC BY)

SoaresC2021anionicFinal published version, 1.65 MBLicence: Creative Commons: Attribution (CC BY)

Cite this

Soares, C., Silván, B., Choi, Y.-S., Celorrio, V., Seymour, V. R., Cibin, G., Griffin, J. M., Scanlon, D. O., & Tapia-Ruiz, N. (2022). Na_2.4Al_0.4Mn_2.6O₇ anionic redox cathode material for sodium-ion batteries – a combined experimental and theoretical approach to elucidate its charge storage mechanism. Journal of Materials Chemistry A, 10(13), 7341-7356. https://doi.org/10.1039/D1TA05137G

@article{be94f0d6e15c4be8ba2f5eb56f26c3b5,

title = "Na2.4Al0.4Mn2.6O7 anionic redox cathode material for sodium-ion batteries – a combined experimental and theoretical approach to elucidate its charge storage mechanism",

abstract = "Here we report the synthesis via ceramic methods of the high-performance Mn-rich Na2.4Al0.4Mn2.6O7 oxygen-redox cathode material for Na-ion batteries, which we use as a testbed material to study the effects of Al substitution and subsequent Na excess in the high-capacity, anionic redox-based cathode material, Na2Mn3O7. The material shows a stable electrochemical performance, with a specific capacity of 215 mA h g−1 in the 1.5–4.7 V voltage range at C/20 and a capacity retention of 90% after 40 cycles. Using a combination of electrochemical and structural analysis together with hybrid density functional theory calculations we explain the behaviour of this material with changes in Mn/anionic redox reactions and associated O2 release reactions occurring during electrochemical cycling (Na+ ion insertion/extraction), and compare these findings to Na2Mn3O7. We expect that these results will advance understanding of the effect of dopants in Mn-rich cathode materials with oxygen redox activity to pave their way towards high-performance sodium-ion batteries.",

author = "Cindy Soares and Bego{\~n}a Silv{\'a}n and Yong-Seok Choi and Veronica Celorrio and Seymour, {Valerie R.} and Giannantonio Cibin and Griffin, {John M.} and Scanlon, {David O.} and Nuria Tapia-Ruiz",

note = "Acknowledgments: NTR would like to thank Lancaster University, the Royal Society (RG170150) and the Faraday Institution (FIRG018) for financial support. We acknowledge the Science and Technology Facilities Council (STFC) for access to B18 beamtime at the Diamond Light Source (SP21847). YC and DOS are grateful to the Faraday Institution for funding the MICHAEL computing cluster hosted at University College London (UCL). The calculations have been also carried out on the Myriad (Myriad@UCL), Young (Young@UCL), and Kathleen (Kathleen@UCL) High Performance Computing Facility provisioned by UCL. Via our membership of the UKs HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202, EP/R029431), this work used the ARCHER UK National Supercomputing Service (http://www.archer.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).",

year = "2022",

month = apr,

day = "7",

doi = "10.1039/D1TA05137G",

language = "English",

volume = "10",

pages = "7341--7356",

journal = "Journal of Materials Chemistry A",

issn = "2050-7488",

publisher = "Royal Society of Chemistry",

number = "13",

}

Soares, C, Silván, B, Choi, Y-S, Celorrio, V, Seymour, VR, Cibin, G, Griffin, JM, Scanlon, DO & Tapia-Ruiz, N 2022, 'Na_2.4Al_0.4Mn_2.6O₇ anionic redox cathode material for sodium-ion batteries – a combined experimental and theoretical approach to elucidate its charge storage mechanism', Journal of Materials Chemistry A, vol. 10, no. 13, pp. 7341-7356. https://doi.org/10.1039/D1TA05137G

Na_2.4Al_0.4Mn_2.6O₇ anionic redox cathode material for sodium-ion batteries – a combined experimental and theoretical approach to elucidate its charge storage mechanism. / Soares, Cindy; Silván, Begoña; Choi, Yong-Seok et al.
In: Journal of Materials Chemistry A, Vol. 10, No. 13, 07.04.2022, p. 7341-7356.

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

TY - JOUR

T1 - Na2.4Al0.4Mn2.6O7 anionic redox cathode material for sodium-ion batteries – a combined experimental and theoretical approach to elucidate its charge storage mechanism

AU - Soares, Cindy

AU - Silván, Begoña

AU - Choi, Yong-Seok

AU - Celorrio, Veronica

AU - Seymour, Valerie R.

AU - Cibin, Giannantonio

AU - Griffin, John M.

AU - Scanlon, David O.

AU - Tapia-Ruiz, Nuria

N1 - Acknowledgments: NTR would like to thank Lancaster University, the Royal Society (RG170150) and the Faraday Institution (FIRG018) for financial support. We acknowledge the Science and Technology Facilities Council (STFC) for access to B18 beamtime at the Diamond Light Source (SP21847). YC and DOS are grateful to the Faraday Institution for funding the MICHAEL computing cluster hosted at University College London (UCL). The calculations have been also carried out on the Myriad (Myriad@UCL), Young (Young@UCL), and Kathleen (Kathleen@UCL) High Performance Computing Facility provisioned by UCL. Via our membership of the UKs HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202, EP/R029431), this work used the ARCHER UK National Supercomputing Service (http://www.archer.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).

PY - 2022/4/7

Y1 - 2022/4/7

N2 - Here we report the synthesis via ceramic methods of the high-performance Mn-rich Na2.4Al0.4Mn2.6O7 oxygen-redox cathode material for Na-ion batteries, which we use as a testbed material to study the effects of Al substitution and subsequent Na excess in the high-capacity, anionic redox-based cathode material, Na2Mn3O7. The material shows a stable electrochemical performance, with a specific capacity of 215 mA h g−1 in the 1.5–4.7 V voltage range at C/20 and a capacity retention of 90% after 40 cycles. Using a combination of electrochemical and structural analysis together with hybrid density functional theory calculations we explain the behaviour of this material with changes in Mn/anionic redox reactions and associated O2 release reactions occurring during electrochemical cycling (Na+ ion insertion/extraction), and compare these findings to Na2Mn3O7. We expect that these results will advance understanding of the effect of dopants in Mn-rich cathode materials with oxygen redox activity to pave their way towards high-performance sodium-ion batteries.

AB - Here we report the synthesis via ceramic methods of the high-performance Mn-rich Na2.4Al0.4Mn2.6O7 oxygen-redox cathode material for Na-ion batteries, which we use as a testbed material to study the effects of Al substitution and subsequent Na excess in the high-capacity, anionic redox-based cathode material, Na2Mn3O7. The material shows a stable electrochemical performance, with a specific capacity of 215 mA h g−1 in the 1.5–4.7 V voltage range at C/20 and a capacity retention of 90% after 40 cycles. Using a combination of electrochemical and structural analysis together with hybrid density functional theory calculations we explain the behaviour of this material with changes in Mn/anionic redox reactions and associated O2 release reactions occurring during electrochemical cycling (Na+ ion insertion/extraction), and compare these findings to Na2Mn3O7. We expect that these results will advance understanding of the effect of dopants in Mn-rich cathode materials with oxygen redox activity to pave their way towards high-performance sodium-ion batteries.

U2 - 10.1039/D1TA05137G

DO - 10.1039/D1TA05137G

M3 - Article

SN - 2050-7488

VL - 10

SP - 7341

EP - 7356

JO - Journal of Materials Chemistry A

JF - Journal of Materials Chemistry A

IS - 13

ER -