Delocalized electron holes on oxygen in a battery cathode

Robert A. House; Gregory J. Rees; Kit McColl; John Joseph Marie; Mirian Garcia-Fernandez; Abhishek Nag; Ke Jin Zhou; Simon Cassidy; Benjamin J. Morgan; M. Saiful Islam; Peter G. Bruce

doi:10.1038/s41560-023-01211-0

Delocalized electron holes on oxygen in a battery cathode

Robert A. House, Gregory J. Rees, Kit McColl, John Joseph Marie, Mirian Garcia-Fernandez, Abhishek Nag, Ke Jin Zhou, Simon Cassidy, Benjamin J. Morgan, M. Saiful Islam, Peter G. Bruce

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

82 Citations (SciVal)

434 Downloads (Pure)

Abstract

Oxide ions in transition metal oxide cathodes can store charge at high voltage offering a route towards higher energy density batteries. However, upon charging these cathodes, the oxidized oxide ions condense to form molecular O₂ trapped in the material. Consequently, the discharge voltage is much lower than charge, leading to undesirable voltage hysteresis. Here we capture the nature of the electron holes on O²⁻ before O₂ formation by exploiting the suppressed transition metal rearrangement in ribbon-ordered Na_0.6[Li_0.2Mn_0.8]O₂. We show that the electron holes formed are delocalized across the oxide ions coordinated to two Mn (O–Mn₂) arranged in ribbons in the transition metal layers. Furthermore, we track these delocalized hole states as they gradually localize in the structure in the form of trapped molecular O₂ over a period of days. Establishing the nature of hole states on oxide ions is important if truly reversible high-voltage O-redox cathodes are to be realized.

Original language	English
Pages (from-to)	351-360
Number of pages	10
Journal	Nature Energy
Volume	8
Issue number	4
DOIs	https://doi.org/10.1038/s41560-023-01211-0
Publication status	Published - 16 Feb 2023

Bibliographical note

Funding Information:
We are indebted to the Engineering and Physical Sciences Research Council (EPSRC), the Henry Royce Institute for Advanced Materials (EP/R00661X/1, EP/S019367/1, EP/R010145/1, EP/L019469/1) and the Faraday Institution (FIRG007, FIRG008, FIRG016) for financial support. We thank the HEC Materials Chemistry Consortium (EP/R029431/1) for supercomputer facilities. We acknowledge Diamond Light Source for time on I21 under proposal MM25589-1. This project was supported by the Royal Academy of Engineering under the Research Fellowship scheme. B.J.M. acknowledges support from the Royal Society (UF130329 and URF\R\191006).

Data availability
All the data generated or analysed during this study are included in the published article and its Supplementary Information. Source data are provided with this paper.

For the purpose of open access, the author has applied a CC BY public copyright licence to any author accepted manuscript (AAM) version arising from this submission.

Funding

We are indebted to the Engineering and Physical Sciences Research Council (EPSRC), the Henry Royce Institute for Advanced Materials (EP/R00661X/1, EP/S019367/1, EP/R010145/1, EP/L019469/1) and the Faraday Institution (FIRG007, FIRG008, FIRG016) for financial support. We thank the HEC Materials Chemistry Consortium (EP/R029431/1) for supercomputer facilities. We acknowledge Diamond Light Source for time on I21 under proposal MM25589-1. This project was supported by the Royal Academy of Engineering under the Research Fellowship scheme. B.J.M. acknowledges support from the Royal Society (UF130329 and URF\R\191006). For the purpose of open access, the author has applied a CC BY public copyright licence to any author accepted manuscript (AAM) version arising from this submission.

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
Renewable Energy, Sustainability and the Environment
Fuel Technology
Energy Engineering and Power Technology

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1038/s41560-023-01211-0

Accepted author manuscript
This version of the article has been accepted for publication, after peer review (when applicable) and is subject to Springer Nature’s AM terms of use, but is not the Version of Record and does not reflect post-acceptance improvements, or any corrections. The Version of Record is available online at: http://dx.doi.org/10.1038/s41560-023-01211-0
Accepted author manuscript, 2.28 MBLicence: CC BY

Cite this

@article{791593c31b7e498792003a826b992426,

title = "Delocalized electron holes on oxygen in a battery cathode",

abstract = "Oxide ions in transition metal oxide cathodes can store charge at high voltage offering a route towards higher energy density batteries. However, upon charging these cathodes, the oxidized oxide ions condense to form molecular O2 trapped in the material. Consequently, the discharge voltage is much lower than charge, leading to undesirable voltage hysteresis. Here we capture the nature of the electron holes on O2− before O2 formation by exploiting the suppressed transition metal rearrangement in ribbon-ordered Na0.6[Li0.2Mn0.8]O2. We show that the electron holes formed are delocalized across the oxide ions coordinated to two Mn (O–Mn2) arranged in ribbons in the transition metal layers. Furthermore, we track these delocalized hole states as they gradually localize in the structure in the form of trapped molecular O2 over a period of days. Establishing the nature of hole states on oxide ions is important if truly reversible high-voltage O-redox cathodes are to be realized.",

author = "House, {Robert A.} and Rees, {Gregory J.} and Kit McColl and Marie, {John Joseph} and Mirian Garcia-Fernandez and Abhishek Nag and Zhou, {Ke Jin} and Simon Cassidy and Morgan, {Benjamin J.} and {Saiful Islam}, M. and Bruce, {Peter G.}",

note = "Funding Information: We are indebted to the Engineering and Physical Sciences Research Council (EPSRC), the Henry Royce Institute for Advanced Materials (EP/R00661X/1, EP/S019367/1, EP/R010145/1, EP/L019469/1) and the Faraday Institution (FIRG007, FIRG008, FIRG016) for financial support. We thank the HEC Materials Chemistry Consortium (EP/R029431/1) for supercomputer facilities. We acknowledge Diamond Light Source for time on I21 under proposal MM25589-1. This project was supported by the Royal Academy of Engineering under the Research Fellowship scheme. B.J.M. acknowledges support from the Royal Society (UF130329 and URF\R\191006). Data availability All the data generated or analysed during this study are included in the published article and its Supplementary Information. Source data are provided with this paper. For the purpose of open access, the author has applied a CC BY public copyright licence to any author accepted manuscript (AAM) version arising from this submission. ",

year = "2023",

month = feb,

day = "16",

doi = "10.1038/s41560-023-01211-0",

language = "English",

volume = "8",

pages = "351--360",

journal = "Nature Energy",

issn = "2058-7546",

publisher = "Springer Nature",

number = "4",

}

TY - JOUR

T1 - Delocalized electron holes on oxygen in a battery cathode

AU - House, Robert A.

AU - Rees, Gregory J.

AU - McColl, Kit

AU - Marie, John Joseph

AU - Garcia-Fernandez, Mirian

AU - Nag, Abhishek

AU - Zhou, Ke Jin

AU - Cassidy, Simon

AU - Morgan, Benjamin J.

AU - Saiful Islam, M.

AU - Bruce, Peter G.

N1 - Funding Information: We are indebted to the Engineering and Physical Sciences Research Council (EPSRC), the Henry Royce Institute for Advanced Materials (EP/R00661X/1, EP/S019367/1, EP/R010145/1, EP/L019469/1) and the Faraday Institution (FIRG007, FIRG008, FIRG016) for financial support. We thank the HEC Materials Chemistry Consortium (EP/R029431/1) for supercomputer facilities. We acknowledge Diamond Light Source for time on I21 under proposal MM25589-1. This project was supported by the Royal Academy of Engineering under the Research Fellowship scheme. B.J.M. acknowledges support from the Royal Society (UF130329 and URF\R\191006). Data availability All the data generated or analysed during this study are included in the published article and its Supplementary Information. Source data are provided with this paper. For the purpose of open access, the author has applied a CC BY public copyright licence to any author accepted manuscript (AAM) version arising from this submission.

PY - 2023/2/16

Y1 - 2023/2/16

N2 - Oxide ions in transition metal oxide cathodes can store charge at high voltage offering a route towards higher energy density batteries. However, upon charging these cathodes, the oxidized oxide ions condense to form molecular O2 trapped in the material. Consequently, the discharge voltage is much lower than charge, leading to undesirable voltage hysteresis. Here we capture the nature of the electron holes on O2− before O2 formation by exploiting the suppressed transition metal rearrangement in ribbon-ordered Na0.6[Li0.2Mn0.8]O2. We show that the electron holes formed are delocalized across the oxide ions coordinated to two Mn (O–Mn2) arranged in ribbons in the transition metal layers. Furthermore, we track these delocalized hole states as they gradually localize in the structure in the form of trapped molecular O2 over a period of days. Establishing the nature of hole states on oxide ions is important if truly reversible high-voltage O-redox cathodes are to be realized.

AB - Oxide ions in transition metal oxide cathodes can store charge at high voltage offering a route towards higher energy density batteries. However, upon charging these cathodes, the oxidized oxide ions condense to form molecular O2 trapped in the material. Consequently, the discharge voltage is much lower than charge, leading to undesirable voltage hysteresis. Here we capture the nature of the electron holes on O2− before O2 formation by exploiting the suppressed transition metal rearrangement in ribbon-ordered Na0.6[Li0.2Mn0.8]O2. We show that the electron holes formed are delocalized across the oxide ions coordinated to two Mn (O–Mn2) arranged in ribbons in the transition metal layers. Furthermore, we track these delocalized hole states as they gradually localize in the structure in the form of trapped molecular O2 over a period of days. Establishing the nature of hole states on oxide ions is important if truly reversible high-voltage O-redox cathodes are to be realized.

UR - http://www.scopus.com/inward/record.url?scp=85148212631&partnerID=8YFLogxK

U2 - 10.1038/s41560-023-01211-0

DO - 10.1038/s41560-023-01211-0

M3 - Article

AN - SCOPUS:85148212631

SN - 2058-7546

VL - 8

SP - 351

EP - 360

JO - Nature Energy

JF - Nature Energy

IS - 4

ER -

Delocalized electron holes on oxygen in a battery cathode

Abstract

Bibliographical note

Funding

ASJC Scopus subject areas

UN SDGs

Access to Document

Other files and links

Fingerprint

Next Generation Li-ion Cathode Materials (CAT-MAT)

Avance 300 MHz Nuclear Magnetic Resonance (NMR) Spectrometer (1South)

Cite this

Delocalized electron holes on oxygen in a battery cathode

Abstract

Bibliographical note

Funding

ASJC Scopus subject areas

UN SDGs

Access to Document

Other files and links

Fingerprint

Projects

Next Generation Li-ion Cathode Materials (CAT-MAT)

Equipment

Avance 300 MHz Nuclear Magnetic Resonance (NMR) Spectrometer (1South)

Cite this