Chemical modulation of local transition metal environment enables reversible oxygen redox in Mn-based layered cathodes

Muhammad Mominur Rahman; Scott McGuigan; Shaofeng Li; Lina Gao; Dong Hou; Zhijie Yang; Zhengrui Xu; Sang Jun Lee; Cheng Jun Sun; Jue Liu; Xiaojing Huang; Xianghui Xiao; Yong Chu; Sami Sainio; Dennis Nordlund; Xueqian Kong; Yijin Liu; Feng Lin

doi:10.1021/acsenergylett.1c01071

Chemical modulation of local transition metal environment enables reversible oxygen redox in Mn-based layered cathodes

Muhammad Mominur Rahman, Scott McGuigan, Shaofeng Li, Lina Gao, Dong Hou, Zhijie Yang, Zhengrui Xu, Sang Jun Lee, Cheng Jun Sun, Jue Liu, Xiaojing Huang, Xianghui Xiao, Yong Chu, Sami Sainio, Dennis Nordlund, Xueqian Kong, Yijin Liu, Feng Lin

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Abstract

Oxygen redox plays a prominent role in enhancing the energy density of Mn-based layered cathodes. However, understanding the factors affecting the reversibility of oxygen redox is nontrivial due to complicated structural and chemical transformations. Herein, we show that local Mn-O symmetry induced structural/chemical evolutions majorly dictate the reversibility of oxygen redox of NaxLiyMn1-yO2 in Na cells. NaxLiyMn1-yO2 with Jahn-Teller distorted MnO6 octahedra undergoes severe Mn dissolution during cycling, which destabilizes the transition metal layer resulting in poor Li retention and irreversible oxygen redox. Jahn-Teller distortion of MnO6 octahedra can be suppressed by modulating the local charge of Mn and Mn-O distance through Mg/Ti dual doping. This leads to reduced Mn dissolution and more reversible oxygen redox. Such stabilization significantly improves the electrochemical performance of Mg/Ti dual doped NaxLiyMn1-yO2. Through this work, we show that local structural stabilization through local chemical environment modification can promote reversible oxygen redox in layered cathodes.

Original language	English
Pages (from-to)	2882-2890
Number of pages	9
Journal	ACS Energy Letters
Volume	6
DOIs	https://doi.org/10.1021/acsenergylett.1c01071
State	Published - 2021

Funding

The work was supported by the National Science Foundation under no. CBET 1912885, as well as Virginia Tech College of Science Lay Nam Chang Dean’s Discovery Fund. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-76SF00515. This research used resources of the Advanced Photon Source; a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Use of the resources of the National Synchrotron Light Source II is supported by Department of Energy (DOE), Office of Science User Facility operated for the DOE Office of Science by the Brookhaven National Laboratory under Contract No. DE-SC0012704. A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. The authors thank Stephanie Spence for data discussion. The authors also thank Dr. Yan-Yan Hu for the scientific discussion. The work was supported by the National Science Foundation under no. CBET 1912885, as well as Virginia Tech College of Science Lay Nam Chang Dean's Discovery Fund. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-76SF00515. This research used resources of the Advanced Photon Source; a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Use of the resources of the National Synchrotron Light Source II is supported by Department of Energy (DOE), Office of Science User Facility operated for the DOE Office of Science by the Brookhaven National Laboratory under Contract No. DESC0012704. A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. The authors thank Stephanie Spence for data discussion. The authors also thank Dr. Yan-Yan Hu for the scientific discussion.

Funders	Funder number
Virginia Tech College of Science Lay Nam Chang Dean's Discovery Fund
Virginia Tech College of Science Lay Nam Chang Dean’s Discovery Fund
National Science Foundation	CBET 1912885
U.S. Department of Energy
Office of Science
Basic Energy Sciences	DE-AC02-76SF00515
Argonne National Laboratory	DE-AC02-06CH11357
Oak Ridge National Laboratory
Brookhaven National Laboratory	DE-SC0012704

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10.1021/acsenergylett.1c01071

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Rahman, M. M., McGuigan, S., Li, S., Gao, L., Hou, D., Yang, Z., Xu, Z., Lee, S. J., Sun, C. J., Liu, J., Huang, X., Xiao, X., Chu, Y., Sainio, S., Nordlund, D., Kong, X., Liu, Y., & Lin, F. (2021). Chemical modulation of local transition metal environment enables reversible oxygen redox in Mn-based layered cathodes. ACS Energy Letters, 6, 2882-2890. https://doi.org/10.1021/acsenergylett.1c01071

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title = "Chemical modulation of local transition metal environment enables reversible oxygen redox in Mn-based layered cathodes",

abstract = "Oxygen redox plays a prominent role in enhancing the energy density of Mn-based layered cathodes. However, understanding the factors affecting the reversibility of oxygen redox is nontrivial due to complicated structural and chemical transformations. Herein, we show that local Mn-O symmetry induced structural/chemical evolutions majorly dictate the reversibility of oxygen redox of NaxLiyMn1-yO2 in Na cells. NaxLiyMn1-yO2 with Jahn-Teller distorted MnO6 octahedra undergoes severe Mn dissolution during cycling, which destabilizes the transition metal layer resulting in poor Li retention and irreversible oxygen redox. Jahn-Teller distortion of MnO6 octahedra can be suppressed by modulating the local charge of Mn and Mn-O distance through Mg/Ti dual doping. This leads to reduced Mn dissolution and more reversible oxygen redox. Such stabilization significantly improves the electrochemical performance of Mg/Ti dual doped NaxLiyMn1-yO2. Through this work, we show that local structural stabilization through local chemical environment modification can promote reversible oxygen redox in layered cathodes.",

author = "Rahman, {Muhammad Mominur} and Scott McGuigan and Shaofeng Li and Lina Gao and Dong Hou and Zhijie Yang and Zhengrui Xu and Lee, {Sang Jun} and Sun, {Cheng Jun} and Jue Liu and Xiaojing Huang and Xianghui Xiao and Yong Chu and Sami Sainio and Dennis Nordlund and Xueqian Kong and Yijin Liu and Feng Lin",

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year = "2021",

doi = "10.1021/acsenergylett.1c01071",

language = "English",

volume = "6",

pages = "2882--2890",

journal = "ACS Energy Letters",

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Rahman, MM, McGuigan, S, Li, S, Gao, L, Hou, D, Yang, Z, Xu, Z, Lee, SJ, Sun, CJ, Liu, J, Huang, X, Xiao, X, Chu, Y, Sainio, S, Nordlund, D, Kong, X, Liu, Y & Lin, F 2021, 'Chemical modulation of local transition metal environment enables reversible oxygen redox in Mn-based layered cathodes', ACS Energy Letters, vol. 6, pp. 2882-2890. https://doi.org/10.1021/acsenergylett.1c01071

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T1 - Chemical modulation of local transition metal environment enables reversible oxygen redox in Mn-based layered cathodes

AU - Rahman, Muhammad Mominur

AU - McGuigan, Scott

AU - Li, Shaofeng

AU - Gao, Lina

AU - Hou, Dong

AU - Yang, Zhijie

AU - Xu, Zhengrui

AU - Lee, Sang Jun

AU - Sun, Cheng Jun

AU - Liu, Jue

AU - Huang, Xiaojing

AU - Xiao, Xianghui

AU - Chu, Yong

AU - Sainio, Sami

AU - Nordlund, Dennis

AU - Kong, Xueqian

AU - Liu, Yijin

AU - Lin, Feng

PY - 2021

Y1 - 2021

N2 - Oxygen redox plays a prominent role in enhancing the energy density of Mn-based layered cathodes. However, understanding the factors affecting the reversibility of oxygen redox is nontrivial due to complicated structural and chemical transformations. Herein, we show that local Mn-O symmetry induced structural/chemical evolutions majorly dictate the reversibility of oxygen redox of NaxLiyMn1-yO2 in Na cells. NaxLiyMn1-yO2 with Jahn-Teller distorted MnO6 octahedra undergoes severe Mn dissolution during cycling, which destabilizes the transition metal layer resulting in poor Li retention and irreversible oxygen redox. Jahn-Teller distortion of MnO6 octahedra can be suppressed by modulating the local charge of Mn and Mn-O distance through Mg/Ti dual doping. This leads to reduced Mn dissolution and more reversible oxygen redox. Such stabilization significantly improves the electrochemical performance of Mg/Ti dual doped NaxLiyMn1-yO2. Through this work, we show that local structural stabilization through local chemical environment modification can promote reversible oxygen redox in layered cathodes.

AB - Oxygen redox plays a prominent role in enhancing the energy density of Mn-based layered cathodes. However, understanding the factors affecting the reversibility of oxygen redox is nontrivial due to complicated structural and chemical transformations. Herein, we show that local Mn-O symmetry induced structural/chemical evolutions majorly dictate the reversibility of oxygen redox of NaxLiyMn1-yO2 in Na cells. NaxLiyMn1-yO2 with Jahn-Teller distorted MnO6 octahedra undergoes severe Mn dissolution during cycling, which destabilizes the transition metal layer resulting in poor Li retention and irreversible oxygen redox. Jahn-Teller distortion of MnO6 octahedra can be suppressed by modulating the local charge of Mn and Mn-O distance through Mg/Ti dual doping. This leads to reduced Mn dissolution and more reversible oxygen redox. Such stabilization significantly improves the electrochemical performance of Mg/Ti dual doped NaxLiyMn1-yO2. Through this work, we show that local structural stabilization through local chemical environment modification can promote reversible oxygen redox in layered cathodes.

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VL - 6

SP - 2882

EP - 2890

JO - ACS Energy Letters

JF - ACS Energy Letters

ER -

Chemical modulation of local transition metal environment enables reversible oxygen redox in Mn-based layered cathodes

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