Characterizing the Structure and Phase Transition of Li2RuO3 Using Variable-Temperature 17O and 7Li NMR Spectroscopy

Philip J. Reeves; Ieuan D. Seymour; Kent J. Griffith; Clare P. Grey

doi:10.1021/acs.chemmater.8b05178

Characterizing the Structure and Phase Transition of Li₂RuO₃ Using Variable-Temperature ¹⁷O and ⁷Li NMR Spectroscopy

Philip J. Reeves, Ieuan D. Seymour, Kent J. Griffith, Clare P. Grey^* (Corresponding Author)

^*Corresponding author for this work

Chemistry

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

21 Citations (Scopus)

Abstract

Li-excess lithium-ion battery cathode materials and the role that reversible anionic redox may play in their high capacities have generated significant interest, motivating studies of the oxygen local structure. Li₂RuO₃ is an intriguing Li-excess model compound, which is studied here by local (⁷Li and ¹⁷O MAS NMR) and long-range (X-ray and neutron diffraction) structural probes. Li₂RuO₃ is often reported as adopting the C2/m or the C/2c space group, which ignores the important role that Ru-Ru dimerization plays in controlling its properties. ¹⁷O NMR reveals four oxygen sites confirming the room-temperature P2₁/m structure proposed by Miura, Y.; Yasui, Y.; Sato, M.; Igawa, N.; Kakurai, K. J. Phys. Soc. Japan 2007, 76, 033705. Through the rationalization of the ¹⁷O NMR shifts, at room temperature and through the phase transition (>260 °C), detailed information concerning the electronic structure and locations of the unpaired electrons in this compound is revealed.

Original language	English
Pages (from-to)	2814-2821
Number of pages	8
Journal	Chemistry of Materials
Volume	31
Issue number	8
Early online date	11 Mar 2019
DOIs	https://doi.org/10.1021/acs.chemmater.8b05178
Publication status	Published - 23 Apr 2019

Bibliographical note

Funding Information:
C.P.G., I.D.S., and P.J.R. acknowledge the NorthEast Center for Chemical Energy Storage (NECCES), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under award DE-SC0012583. This work is based upon experiments performed at the SPODI instrument operated by KIT and TUM at the Heinz Maier-Leibnitz Zentrum (MLZ), Garching, Germany. K.J.G. gratefully acknowledges the financial support provided by TUM to perform the neutron scattering measurements and experimental support from beamline scientist Anatoliy Senyshyn. K.J.G. also thanks the EPSRC (EP/M009521/1) for funding. The authors thank Dr. Sian Dutton and Michael Hope for useful discussions and Dr. Matthew Dunstan for help with the high temperature NMR spectroscopy.

Data Availability Statement

No data availability statement

Keywords

Chemical structure
Materials
Oxygen
Phase transitions
Quantum mechanics

UN SDGs

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

Access to Document

10.1021/acs.chemmater.8b05178Licence: Unspecified

Cite this

@article{b97330f8403e43e493c0cc5f144860a8,

title = "Characterizing the Structure and Phase Transition of Li2RuO3 Using Variable-Temperature 17O and 7Li NMR Spectroscopy",

abstract = "Li-excess lithium-ion battery cathode materials and the role that reversible anionic redox may play in their high capacities have generated significant interest, motivating studies of the oxygen local structure. Li2RuO3 is an intriguing Li-excess model compound, which is studied here by local (7Li and 17O MAS NMR) and long-range (X-ray and neutron diffraction) structural probes. Li2RuO3 is often reported as adopting the C2/m or the C/2c space group, which ignores the important role that Ru-Ru dimerization plays in controlling its properties. 17O NMR reveals four oxygen sites confirming the room-temperature P21/m structure proposed by Miura, Y.; Yasui, Y.; Sato, M.; Igawa, N.; Kakurai, K. J. Phys. Soc. Japan 2007, 76, 033705. Through the rationalization of the 17O NMR shifts, at room temperature and through the phase transition (>260 °C), detailed information concerning the electronic structure and locations of the unpaired electrons in this compound is revealed.",

keywords = "Chemical structure, Materials, Oxygen, Phase transitions, Quantum mechanics",

author = "Reeves, {Philip J.} and Seymour, {Ieuan D.} and Griffith, {Kent J.} and Grey, {Clare P.}",

note = "Funding Information: C.P.G., I.D.S., and P.J.R. acknowledge the NorthEast Center for Chemical Energy Storage (NECCES), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under award DE-SC0012583. This work is based upon experiments performed at the SPODI instrument operated by KIT and TUM at the Heinz Maier-Leibnitz Zentrum (MLZ), Garching, Germany. K.J.G. gratefully acknowledges the financial support provided by TUM to perform the neutron scattering measurements and experimental support from beamline scientist Anatoliy Senyshyn. K.J.G. also thanks the EPSRC (EP/M009521/1) for funding. The authors thank Dr. Sian Dutton and Michael Hope for useful discussions and Dr. Matthew Dunstan for help with the high temperature NMR spectroscopy.",

year = "2019",

month = apr,

day = "23",

doi = "10.1021/acs.chemmater.8b05178",

language = "English",

volume = "31",

pages = "2814--2821",

journal = "Chemistry of Materials",

issn = "0897-4756",

publisher = "American Chemical Society",

number = "8",

}

TY - JOUR

T1 - Characterizing the Structure and Phase Transition of Li2RuO3 Using Variable-Temperature 17O and 7Li NMR Spectroscopy

AU - Reeves, Philip J.

AU - Seymour, Ieuan D.

AU - Griffith, Kent J.

AU - Grey, Clare P.

N1 - Funding Information: C.P.G., I.D.S., and P.J.R. acknowledge the NorthEast Center for Chemical Energy Storage (NECCES), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under award DE-SC0012583. This work is based upon experiments performed at the SPODI instrument operated by KIT and TUM at the Heinz Maier-Leibnitz Zentrum (MLZ), Garching, Germany. K.J.G. gratefully acknowledges the financial support provided by TUM to perform the neutron scattering measurements and experimental support from beamline scientist Anatoliy Senyshyn. K.J.G. also thanks the EPSRC (EP/M009521/1) for funding. The authors thank Dr. Sian Dutton and Michael Hope for useful discussions and Dr. Matthew Dunstan for help with the high temperature NMR spectroscopy.

PY - 2019/4/23

Y1 - 2019/4/23

N2 - Li-excess lithium-ion battery cathode materials and the role that reversible anionic redox may play in their high capacities have generated significant interest, motivating studies of the oxygen local structure. Li2RuO3 is an intriguing Li-excess model compound, which is studied here by local (7Li and 17O MAS NMR) and long-range (X-ray and neutron diffraction) structural probes. Li2RuO3 is often reported as adopting the C2/m or the C/2c space group, which ignores the important role that Ru-Ru dimerization plays in controlling its properties. 17O NMR reveals four oxygen sites confirming the room-temperature P21/m structure proposed by Miura, Y.; Yasui, Y.; Sato, M.; Igawa, N.; Kakurai, K. J. Phys. Soc. Japan 2007, 76, 033705. Through the rationalization of the 17O NMR shifts, at room temperature and through the phase transition (>260 °C), detailed information concerning the electronic structure and locations of the unpaired electrons in this compound is revealed.

AB - Li-excess lithium-ion battery cathode materials and the role that reversible anionic redox may play in their high capacities have generated significant interest, motivating studies of the oxygen local structure. Li2RuO3 is an intriguing Li-excess model compound, which is studied here by local (7Li and 17O MAS NMR) and long-range (X-ray and neutron diffraction) structural probes. Li2RuO3 is often reported as adopting the C2/m or the C/2c space group, which ignores the important role that Ru-Ru dimerization plays in controlling its properties. 17O NMR reveals four oxygen sites confirming the room-temperature P21/m structure proposed by Miura, Y.; Yasui, Y.; Sato, M.; Igawa, N.; Kakurai, K. J. Phys. Soc. Japan 2007, 76, 033705. Through the rationalization of the 17O NMR shifts, at room temperature and through the phase transition (>260 °C), detailed information concerning the electronic structure and locations of the unpaired electrons in this compound is revealed.

KW - Chemical structure

KW - Materials

KW - Oxygen

KW - Phase transitions

KW - Quantum mechanics

UR - http://www.scopus.com/inward/record.url?scp=85065621530&partnerID=8YFLogxK

U2 - 10.1021/acs.chemmater.8b05178

DO - 10.1021/acs.chemmater.8b05178

M3 - Article

AN - SCOPUS:85065621530

SN - 0897-4756

VL - 31

SP - 2814

EP - 2821

JO - Chemistry of Materials

JF - Chemistry of Materials

IS - 8

ER -