Structure-Induced Reversible Anionic Redox Activity in Na Layered Oxide Cathode

Xiaohui Rong; Jue Liu; Enyuan Hu; Yijin Liu; Yi Wang; Jinpeng Wu; Xiqian Yu; Katharine Page; Yong Sheng Hu; Wanli Yang; Hong Li; Xiao Qing Yang; Liquan Chen; Xuejie Huang

doi:10.1016/j.joule.2017.10.008

Structure-Induced Reversible Anionic Redox Activity in Na Layered Oxide Cathode

Xiaohui Rong, Jue Liu, Enyuan Hu, Yijin Liu, Yi Wang, Jinpeng Wu, Xiqian Yu, Katharine Page, Yong Sheng Hu, Wanli Yang, Hong Li, Xiao Qing Yang, Liquan Chen, Xuejie Huang

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Abstract

Anionic redox reaction (ARR) in lithium- and sodium-ion batteries is under hot discussion, mainly regarding how oxygen anion participates and to what extent oxygen can be reversibly oxidized and reduced. Here, a P3-type Na_0.6[Li_0.2Mn_0.8]O₂ with reversible capacity from pure ARR was studied. The interlayer O-O distance (peroxo-like O-O dimer, 2.506(3) Å), associated with oxidization of oxygen anions, was directly detected by using a neutron total scattering technique. Different from Li₂RuO₃ or Li₂IrO₃ with strong metal-oxygen (M-O) bonding, for P3-type Na_0.6[Li_0.2Mn_0.8]O₂ with relatively weak Mn-O covalent bonding, crystal structure factors might play an even more important role in stabilizing the oxidized species, as both Li and Mn ions are immobile in the structure and thus may inhibit the irreversible transformation of the oxidized species to O₂ gas. Utilization of anionic redox reaction (ARR) on oxygen has been considered as an effective way to promote the charge-discharge capacity of the layered oxide cathodes for lithium- or sodium-ion batteries. The detailed mechanism of ARR, in particular how crystal structure affects and coordinates with the ARR, is not yet well understood. In the present work, a combination of X-ray and neutron total scattering measurements has been performed to study the structure of the prototype P3-type layered Na_0.6[Li_0.2Mn_0.8]O₂ with pure ARR. Unique structural characteristics, rather than prevailing knowledge of covalency of metal-oxygen, enable the stabilization of the crystal structure of Na_0.6[Li_0.2Mn_0.8]O₂ along with the ARR. This work suggests that reversible ARR can be manipulated by proper structure designs, thus to achieve high lithium or sodium storage in layered oxide cathodes. For P3-type Na_0.6[Li_0.2Mn_0.8]O₂ with relatively weak Mn-O covalent bonding, crystal structure factors play an important role in stabilizing the oxidized species, inhibiting the irreversible transformation of the oxidized species to O₂ gas. The finding is important for better design of layered oxide positive materials with higher reversible capacity via the introduction of a reversible anionic redox reaction.

Original language	English
Pages (from-to)	125-140
Number of pages	16
Journal	Joule
Volume	2
Issue number	1
DOIs	https://doi.org/10.1016/j.joule.2017.10.008
State	Published - Jan 17 2018

Funding

The work in Institute of Physics was supported by funding from”973” Projects (2014CB932300), the NSFC (51725206, 11234013, and 51421002), and One Hundred Talent Project of the Chinese Academy of Sciences. Research conducted at the NOMAD beamline at ORNL's Spallation Neutron Source was sponsored by the Scientific User Facilities Division, Office of Basic Sciences, U.S. Department of Energy, under contract no. DE-AC05-00OR22725. The work at Brookhaven National Laboratory was supported by the U.S. Department of Energy, the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies through Advanced Battery Material Research (BMR) program under contract no. DE-SC0012704. This research used resources 28-ID-2 of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under contract no. DE-SC0012704. The authors would like to acknowledge that the research used beamline 17-BM at the Advanced Photon Source (contract no. DE-AC02-06CH11357) and BL14W, BL08U1A at Shanghai Synchrotron Radiation Facility. This research used resources of beamline 8.0.1 of the Advanced Light Source, which is a DOE Office of Science User Facility under contract no. DE-AC02-05CH11231. The authors would also like to acknowledge the use of Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under contract no. DE-AC02-76SF00515. The work in Institute of Physics was supported by funding from ”973” Projects ( 2014CB932300 ), the NSFC ( 51725206 , 11234013 , and 51421002 ), and One Hundred Talent Project of the Chinese Academy of Sciences . Research conducted at the NOMAD beamline at ORNL's Spallation Neutron Source was sponsored by the Scientific User Facilities Division, Office of Basic Sciences, U.S. Department of Energy , under contract no. DE-AC05-00OR22725 . The work at Brookhaven National Laboratory was supported by the U.S. Department of Energy, the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies through Advanced Battery Material Research (BMR) program under contract no. DE-SC0012704. This research used resources 28-ID-2 of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under contract no. DE-SC0012704. The authors would like to acknowledge that the research used beamline 17-BM at the Advanced Photon Source (contract no. DE-AC02-06CH11357) and BL14W, BL08U1A at Shanghai Synchrotron Radiation Facility. This research used resources of beamline 8.0.1 of the Advanced Light Source, which is a DOE Office of Science User Facility under contract no. DE-AC02-05CH11231. The authors would also like to acknowledge the use of Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under contract no. DE-AC02-76SF00515.

Funders	Funder number
DOE Office of Science
Office of Basic Energy Sciences
Office of Basic Sciences
Scientific User Facilities Division
U.S. Department of Energy	DE-AC05-00OR22725
Office of Science
Office of Energy Efficiency and Renewable Energy
Brookhaven National Laboratory
Vehicle Technologies Office
National Natural Science Foundation of China	51421002, 51725206, 11234013
Chinese Academy of Sciences

Keywords

anionic redox
layered oxide cathode
peroxo-like O-O dimer
sodium-ion batteries

UN SDGs

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

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10.1016/j.joule.2017.10.008

Cite this

@article{462da9a2863a495b8ad02ce143aaf322,

title = "Structure-Induced Reversible Anionic Redox Activity in Na Layered Oxide Cathode",

abstract = "Anionic redox reaction (ARR) in lithium- and sodium-ion batteries is under hot discussion, mainly regarding how oxygen anion participates and to what extent oxygen can be reversibly oxidized and reduced. Here, a P3-type Na0.6[Li0.2Mn0.8]O2 with reversible capacity from pure ARR was studied. The interlayer O-O distance (peroxo-like O-O dimer, 2.506(3) {\AA}), associated with oxidization of oxygen anions, was directly detected by using a neutron total scattering technique. Different from Li2RuO3 or Li2IrO3 with strong metal-oxygen (M-O) bonding, for P3-type Na0.6[Li0.2Mn0.8]O2 with relatively weak Mn-O covalent bonding, crystal structure factors might play an even more important role in stabilizing the oxidized species, as both Li and Mn ions are immobile in the structure and thus may inhibit the irreversible transformation of the oxidized species to O2 gas. Utilization of anionic redox reaction (ARR) on oxygen has been considered as an effective way to promote the charge-discharge capacity of the layered oxide cathodes for lithium- or sodium-ion batteries. The detailed mechanism of ARR, in particular how crystal structure affects and coordinates with the ARR, is not yet well understood. In the present work, a combination of X-ray and neutron total scattering measurements has been performed to study the structure of the prototype P3-type layered Na0.6[Li0.2Mn0.8]O2 with pure ARR. Unique structural characteristics, rather than prevailing knowledge of covalency of metal-oxygen, enable the stabilization of the crystal structure of Na0.6[Li0.2Mn0.8]O2 along with the ARR. This work suggests that reversible ARR can be manipulated by proper structure designs, thus to achieve high lithium or sodium storage in layered oxide cathodes. For P3-type Na0.6[Li0.2Mn0.8]O2 with relatively weak Mn-O covalent bonding, crystal structure factors play an important role in stabilizing the oxidized species, inhibiting the irreversible transformation of the oxidized species to O2 gas. The finding is important for better design of layered oxide positive materials with higher reversible capacity via the introduction of a reversible anionic redox reaction.",

keywords = "anionic redox, layered oxide cathode, peroxo-like O-O dimer, sodium-ion batteries",

author = "Xiaohui Rong and Jue Liu and Enyuan Hu and Yijin Liu and Yi Wang and Jinpeng Wu and Xiqian Yu and Katharine Page and Hu, {Yong Sheng} and Wanli Yang and Hong Li and Yang, {Xiao Qing} and Liquan Chen and Xuejie Huang",

note = "Publisher Copyright: {\textcopyright} 2017 Elsevier Inc.",

year = "2018",

month = jan,

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doi = "10.1016/j.joule.2017.10.008",

language = "English",

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T1 - Structure-Induced Reversible Anionic Redox Activity in Na Layered Oxide Cathode

AU - Rong, Xiaohui

AU - Liu, Jue

AU - Hu, Enyuan

AU - Liu, Yijin

AU - Wang, Yi

AU - Wu, Jinpeng

AU - Yu, Xiqian

AU - Page, Katharine

AU - Hu, Yong Sheng

AU - Yang, Wanli

AU - Li, Hong

AU - Yang, Xiao Qing

AU - Chen, Liquan

AU - Huang, Xuejie

PY - 2018/1/17

Y1 - 2018/1/17

N2 - Anionic redox reaction (ARR) in lithium- and sodium-ion batteries is under hot discussion, mainly regarding how oxygen anion participates and to what extent oxygen can be reversibly oxidized and reduced. Here, a P3-type Na0.6[Li0.2Mn0.8]O2 with reversible capacity from pure ARR was studied. The interlayer O-O distance (peroxo-like O-O dimer, 2.506(3) Å), associated with oxidization of oxygen anions, was directly detected by using a neutron total scattering technique. Different from Li2RuO3 or Li2IrO3 with strong metal-oxygen (M-O) bonding, for P3-type Na0.6[Li0.2Mn0.8]O2 with relatively weak Mn-O covalent bonding, crystal structure factors might play an even more important role in stabilizing the oxidized species, as both Li and Mn ions are immobile in the structure and thus may inhibit the irreversible transformation of the oxidized species to O2 gas. Utilization of anionic redox reaction (ARR) on oxygen has been considered as an effective way to promote the charge-discharge capacity of the layered oxide cathodes for lithium- or sodium-ion batteries. The detailed mechanism of ARR, in particular how crystal structure affects and coordinates with the ARR, is not yet well understood. In the present work, a combination of X-ray and neutron total scattering measurements has been performed to study the structure of the prototype P3-type layered Na0.6[Li0.2Mn0.8]O2 with pure ARR. Unique structural characteristics, rather than prevailing knowledge of covalency of metal-oxygen, enable the stabilization of the crystal structure of Na0.6[Li0.2Mn0.8]O2 along with the ARR. This work suggests that reversible ARR can be manipulated by proper structure designs, thus to achieve high lithium or sodium storage in layered oxide cathodes. For P3-type Na0.6[Li0.2Mn0.8]O2 with relatively weak Mn-O covalent bonding, crystal structure factors play an important role in stabilizing the oxidized species, inhibiting the irreversible transformation of the oxidized species to O2 gas. The finding is important for better design of layered oxide positive materials with higher reversible capacity via the introduction of a reversible anionic redox reaction.

AB - Anionic redox reaction (ARR) in lithium- and sodium-ion batteries is under hot discussion, mainly regarding how oxygen anion participates and to what extent oxygen can be reversibly oxidized and reduced. Here, a P3-type Na0.6[Li0.2Mn0.8]O2 with reversible capacity from pure ARR was studied. The interlayer O-O distance (peroxo-like O-O dimer, 2.506(3) Å), associated with oxidization of oxygen anions, was directly detected by using a neutron total scattering technique. Different from Li2RuO3 or Li2IrO3 with strong metal-oxygen (M-O) bonding, for P3-type Na0.6[Li0.2Mn0.8]O2 with relatively weak Mn-O covalent bonding, crystal structure factors might play an even more important role in stabilizing the oxidized species, as both Li and Mn ions are immobile in the structure and thus may inhibit the irreversible transformation of the oxidized species to O2 gas. Utilization of anionic redox reaction (ARR) on oxygen has been considered as an effective way to promote the charge-discharge capacity of the layered oxide cathodes for lithium- or sodium-ion batteries. The detailed mechanism of ARR, in particular how crystal structure affects and coordinates with the ARR, is not yet well understood. In the present work, a combination of X-ray and neutron total scattering measurements has been performed to study the structure of the prototype P3-type layered Na0.6[Li0.2Mn0.8]O2 with pure ARR. Unique structural characteristics, rather than prevailing knowledge of covalency of metal-oxygen, enable the stabilization of the crystal structure of Na0.6[Li0.2Mn0.8]O2 along with the ARR. This work suggests that reversible ARR can be manipulated by proper structure designs, thus to achieve high lithium or sodium storage in layered oxide cathodes. For P3-type Na0.6[Li0.2Mn0.8]O2 with relatively weak Mn-O covalent bonding, crystal structure factors play an important role in stabilizing the oxidized species, inhibiting the irreversible transformation of the oxidized species to O2 gas. The finding is important for better design of layered oxide positive materials with higher reversible capacity via the introduction of a reversible anionic redox reaction.

KW - anionic redox

KW - layered oxide cathode

KW - peroxo-like O-O dimer

KW - sodium-ion batteries

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Structure-Induced Reversible Anionic Redox Activity in Na Layered Oxide Cathode

Abstract

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Keywords

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