Superstructure and Correlated Na+ Hopping in a Layered Mg-Substituted Sodium Manganate Battery Cathode are Driven by Local Electroneutrality

Euan N Bassey; Ieuan D Seymour; Joshua D Bocarsly; David A Keen; Guido Pintacuda; Clare P Grey

doi:10.1021/acs.chemmater.3c02180

Superstructure and Correlated Na+ Hopping in a Layered Mg-Substituted Sodium Manganate Battery Cathode are Driven by Local Electroneutrality

Euan N Bassey, Ieuan D Seymour, Joshua D Bocarsly, David A Keen, Guido Pintacuda, Clare P Grey^* (Corresponding Author)

^*Corresponding author for this work

Chemistry

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

Abstract

In this work, we present a variable-temperature 23Na NMR and variable-temperature and variable-frequency electron paramagnetic resonance (EPR) analysis of the local structure of a layered P2 Na-ion battery cathode material, Na0.67[Mg0.28Mn0.72]O2 (NMMO). For the first time, we elucidate the superstructure in this material by using synchrotron X-ray diffraction and total neutron scattering and show that this superstructure is consistent with NMR and EPR spectra. To complement our experimental data, we carry out ab initio calculations of the quadrupolar and hyperfine 23Na NMR shifts, the Na+ ion hopping energy barriers, and the EPR g-tensors. We also describe an in-house simulation script for modeling the effects of ionic mobility on variable-temperature NMR spectra and use our simulations to interpret the experimental spectra, available upon request. We find long-zigzag-type Na ordering with two different types of Na sites, one with high mobility and the other with low mobility, and reconcile the tendency toward Na+/vacancy ordering to the preservation of local electroneutrality. The combined magnetic resonance methodology for studying local paramagnetic environments from the perspective of electron and nuclear spins will be useful for examining the local structures of materials for devices.

Original language	English
Pages (from-to)	10564-10583
Number of pages	20
Journal	Chemistry of Materials
Volume	35
Issue number	24
Early online date	7 Dec 2023
DOIs	https://doi.org/10.1021/acs.chemmater.3c02180
Publication status	Published - 26 Dec 2023

Bibliographical note

Acknowledgments
ARTICLE SECTIONSJump To
E.N.B. acknowledges funding from the Engineering Physical Sciences Research Council (EPSRC) via the National Productivity Interest Fund (NPIF) 2018 (EP/S515334/1). J.D.B. acknowledges funding from the Faraday Institution (EP/S003053/1, FIRG016). The authors also thank the Science and Technology Facilities Council (STFC) and ISIS Neutron and Muon source for neutron data (experiment no.: RB2010350). Additional thanks are given to the staff scientists at beamline I11 of the Diamond Light Source for synchrotron data using block allocation group time under proposal CY34243. This work also utilized the ARCHER UK National Supercomputing Service via our membership in the UK’s HEC Materials Chemistry Consortium, funded by the EPSRC (EP/L000202). The research was also carried out at the Center for Functional Nanomaterials, Brookhaven National Laboratory, through the U.S. Department of Energy, Office of Basic Energy Sciences, Contract DE-AC02-98CH10866. E.N.B. would also like to thank A. Van der Ven and M.A. Jones for illuminating discussions.

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Cite this

@article{b69854fb4cdd4d6080a68da8f02117b0,

title = "Superstructure and Correlated Na+ Hopping in a Layered Mg-Substituted Sodium Manganate Battery Cathode are Driven by Local Electroneutrality",

abstract = "In this work, we present a variable-temperature 23Na NMR and variable-temperature and variable-frequency electron paramagnetic resonance (EPR) analysis of the local structure of a layered P2 Na-ion battery cathode material, Na0.67[Mg0.28Mn0.72]O2 (NMMO). For the first time, we elucidate the superstructure in this material by using synchrotron X-ray diffraction and total neutron scattering and show that this superstructure is consistent with NMR and EPR spectra. To complement our experimental data, we carry out ab initio calculations of the quadrupolar and hyperfine 23Na NMR shifts, the Na+ ion hopping energy barriers, and the EPR g-tensors. We also describe an in-house simulation script for modeling the effects of ionic mobility on variable-temperature NMR spectra and use our simulations to interpret the experimental spectra, available upon request. We find long-zigzag-type Na ordering with two different types of Na sites, one with high mobility and the other with low mobility, and reconcile the tendency toward Na+/vacancy ordering to the preservation of local electroneutrality. The combined magnetic resonance methodology for studying local paramagnetic environments from the perspective of electron and nuclear spins will be useful for examining the local structures of materials for devices.",

author = "Bassey, {Euan N} and Seymour, {Ieuan D} and Bocarsly, {Joshua D} and Keen, {David A} and Guido Pintacuda and Grey, {Clare P}",

note = "Acknowledgments ARTICLE SECTIONSJump To E.N.B. acknowledges funding from the Engineering Physical Sciences Research Council (EPSRC) via the National Productivity Interest Fund (NPIF) 2018 (EP/S515334/1). J.D.B. acknowledges funding from the Faraday Institution (EP/S003053/1, FIRG016). The authors also thank the Science and Technology Facilities Council (STFC) and ISIS Neutron and Muon source for neutron data (experiment no.: RB2010350). Additional thanks are given to the staff scientists at beamline I11 of the Diamond Light Source for synchrotron data using block allocation group time under proposal CY34243. This work also utilized the ARCHER UK National Supercomputing Service via our membership in the UK{\textquoteright}s HEC Materials Chemistry Consortium, funded by the EPSRC (EP/L000202). The research was also carried out at the Center for Functional Nanomaterials, Brookhaven National Laboratory, through the U.S. Department of Energy, Office of Basic Energy Sciences, Contract DE-AC02-98CH10866. E.N.B. would also like to thank A. Van der Ven and M.A. Jones for illuminating discussions.",

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T1 - Superstructure and Correlated Na+ Hopping in a Layered Mg-Substituted Sodium Manganate Battery Cathode are Driven by Local Electroneutrality

AU - Bassey, Euan N

AU - Seymour, Ieuan D

AU - Bocarsly, Joshua D

AU - Keen, David A

AU - Pintacuda, Guido

AU - Grey, Clare P

N1 - Acknowledgments ARTICLE SECTIONSJump To E.N.B. acknowledges funding from the Engineering Physical Sciences Research Council (EPSRC) via the National Productivity Interest Fund (NPIF) 2018 (EP/S515334/1). J.D.B. acknowledges funding from the Faraday Institution (EP/S003053/1, FIRG016). The authors also thank the Science and Technology Facilities Council (STFC) and ISIS Neutron and Muon source for neutron data (experiment no.: RB2010350). Additional thanks are given to the staff scientists at beamline I11 of the Diamond Light Source for synchrotron data using block allocation group time under proposal CY34243. This work also utilized the ARCHER UK National Supercomputing Service via our membership in the UK’s HEC Materials Chemistry Consortium, funded by the EPSRC (EP/L000202). The research was also carried out at the Center for Functional Nanomaterials, Brookhaven National Laboratory, through the U.S. Department of Energy, Office of Basic Energy Sciences, Contract DE-AC02-98CH10866. E.N.B. would also like to thank A. Van der Ven and M.A. Jones for illuminating discussions.

PY - 2023/12/26

Y1 - 2023/12/26

N2 - In this work, we present a variable-temperature 23Na NMR and variable-temperature and variable-frequency electron paramagnetic resonance (EPR) analysis of the local structure of a layered P2 Na-ion battery cathode material, Na0.67[Mg0.28Mn0.72]O2 (NMMO). For the first time, we elucidate the superstructure in this material by using synchrotron X-ray diffraction and total neutron scattering and show that this superstructure is consistent with NMR and EPR spectra. To complement our experimental data, we carry out ab initio calculations of the quadrupolar and hyperfine 23Na NMR shifts, the Na+ ion hopping energy barriers, and the EPR g-tensors. We also describe an in-house simulation script for modeling the effects of ionic mobility on variable-temperature NMR spectra and use our simulations to interpret the experimental spectra, available upon request. We find long-zigzag-type Na ordering with two different types of Na sites, one with high mobility and the other with low mobility, and reconcile the tendency toward Na+/vacancy ordering to the preservation of local electroneutrality. The combined magnetic resonance methodology for studying local paramagnetic environments from the perspective of electron and nuclear spins will be useful for examining the local structures of materials for devices.

AB - In this work, we present a variable-temperature 23Na NMR and variable-temperature and variable-frequency electron paramagnetic resonance (EPR) analysis of the local structure of a layered P2 Na-ion battery cathode material, Na0.67[Mg0.28Mn0.72]O2 (NMMO). For the first time, we elucidate the superstructure in this material by using synchrotron X-ray diffraction and total neutron scattering and show that this superstructure is consistent with NMR and EPR spectra. To complement our experimental data, we carry out ab initio calculations of the quadrupolar and hyperfine 23Na NMR shifts, the Na+ ion hopping energy barriers, and the EPR g-tensors. We also describe an in-house simulation script for modeling the effects of ionic mobility on variable-temperature NMR spectra and use our simulations to interpret the experimental spectra, available upon request. We find long-zigzag-type Na ordering with two different types of Na sites, one with high mobility and the other with low mobility, and reconcile the tendency toward Na+/vacancy ordering to the preservation of local electroneutrality. The combined magnetic resonance methodology for studying local paramagnetic environments from the perspective of electron and nuclear spins will be useful for examining the local structures of materials for devices.

U2 - 10.1021/acs.chemmater.3c02180

DO - 10.1021/acs.chemmater.3c02180

M3 - Article

C2 - 38162043

SN - 0897-4756

VL - 35

SP - 10564

EP - 10583

JO - Chemistry of Materials

JF - Chemistry of Materials

IS - 24

ER -

Superstructure and Correlated Na+ Hopping in a Layered Mg-Substituted Sodium Manganate Battery Cathode are Driven by Local Electroneutrality

Abstract

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