Thermal stability in the blended lithium manganese oxide - Lithium nickel cobalt manganese oxide cathode materials: An in situ time-resolved X-Ray diffraction and mass spectroscopy study

Enyuan Hu; Seong Min Bak; Sanjaya D. Senanayake; Xiao Qing Yang; Kyung Wan Nam; Lulu Zhang; Minhua Shao

doi:10.1016/j.jpowsour.2014.12.015

Thermal stability in the blended lithium manganese oxide - Lithium nickel cobalt manganese oxide cathode materials: An in situ time-resolved X-Ray diffraction and mass spectroscopy study

Enyuan Hu, Seong Min Bak, Sanjaya D. Senanayake, Xiao Qing Yang, Kyung Wan Nam, Lulu Zhang, Minhua Shao

Department of Materials Science and Engineering

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

Abstract

Thermal stabilities of a series of blended LiMn₂O₄ (LMO)eLiNi_1/3Co_1/3Mn_1/3O₂ (NCM) cathode materials with different weight ratios were studied by in situ time-resolved X-ray diffraction (XRD) combined with mass spectroscopy in the temperature range of 25 °C-580 °C under helium atmosphere. Upon heating, the electrochemically delithiated LMO changed into Mn₃O₄ phase at around 250 °C. Formation of MnO with rock-salt structure started at 520 °C. This observation is in contrast to the previous report for chemically delithiated LMO in air, in which a process of λ-MnO₂ transforming to β-MnO₂ was observed. Oxygen peak was not observed in all cases, presumably as a result of either consumption by the carbon or detection limit. CO₂ profile correlates well with the phase transition and indirectly suggests the oxygen release of the cathode. Introducing NCM into LMO has two effects: first, it makes the high temperature rock-salt phase formation more complicated with more peaks in CO₂ profile due to different MO (M = Ni, Mn, Co) phases; secondly, the onset temperature of CO₂ release is lowered, implying lowered oxygen release temperature. Upon heating, XRD patterns indicate the NCM part reacts first, followed by the LMO part. This confirms the better thermal stability of LMO over NCM.

Original language	English
Pages (from-to)	193-197
Number of pages	5
Journal	Journal of Power Sources
Volume	277
DOIs	https://doi.org/10.1016/j.jpowsour.2014.12.015
Publication status	Published - 2015 Mar 1

Bibliographical note

Funding Information:
This work was supported by the U.S. Department of Energy, the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies under Contract Number DE-AC02-98CH10886 . Use of the NSLS was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences , under Contract No. DE-AC02-98CH10886 . MS is supported by a start-up grant from the Hong Kong University of Science and Technology . This work was also supported by the Energy Efficiency & Resources of the Korea Institute of Energy Technology Evaluation and Planning grant funded by the Korea government Ministry of Trade, Industry & Energy (Project no. 20142020103090 ). The authors appreciate the invaluable discussion with Prof. Jean-Marie Tarascon.

Publisher Copyright:
© 2014 Elsevier B.V. All rights reserved.

All Science Journal Classification (ASJC) codes

Renewable Energy, Sustainability and the Environment
Energy Engineering and Power Technology
Physical and Theoretical Chemistry
Electrical and Electronic Engineering

UN SDGs

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

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10.1016/j.jpowsour.2014.12.015

Cite this

@article{5f8004c4d9ae4ad594340bd4019ef49c,

title = "Thermal stability in the blended lithium manganese oxide - Lithium nickel cobalt manganese oxide cathode materials: An in situ time-resolved X-Ray diffraction and mass spectroscopy study",

abstract = "Thermal stabilities of a series of blended LiMn2O4 (LMO)eLiNi1/3Co1/3Mn1/3O2 (NCM) cathode materials with different weight ratios were studied by in situ time-resolved X-ray diffraction (XRD) combined with mass spectroscopy in the temperature range of 25 °C-580 °C under helium atmosphere. Upon heating, the electrochemically delithiated LMO changed into Mn3O4 phase at around 250 °C. Formation of MnO with rock-salt structure started at 520 °C. This observation is in contrast to the previous report for chemically delithiated LMO in air, in which a process of λ-MnO2 transforming to β-MnO2 was observed. Oxygen peak was not observed in all cases, presumably as a result of either consumption by the carbon or detection limit. CO2 profile correlates well with the phase transition and indirectly suggests the oxygen release of the cathode. Introducing NCM into LMO has two effects: first, it makes the high temperature rock-salt phase formation more complicated with more peaks in CO2 profile due to different MO (M = Ni, Mn, Co) phases; secondly, the onset temperature of CO2 release is lowered, implying lowered oxygen release temperature. Upon heating, XRD patterns indicate the NCM part reacts first, followed by the LMO part. This confirms the better thermal stability of LMO over NCM.",

author = "Enyuan Hu and Bak, {Seong Min} and Senanayake, {Sanjaya D.} and Yang, {Xiao Qing} and Nam, {Kyung Wan} and Lulu Zhang and Minhua Shao",

note = "Funding Information: This work was supported by the U.S. Department of Energy, the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies under Contract Number DE-AC02-98CH10886 . Use of the NSLS was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences , under Contract No. DE-AC02-98CH10886 . MS is supported by a start-up grant from the Hong Kong University of Science and Technology . This work was also supported by the Energy Efficiency & Resources of the Korea Institute of Energy Technology Evaluation and Planning grant funded by the Korea government Ministry of Trade, Industry & Energy (Project no. 20142020103090 ). The authors appreciate the invaluable discussion with Prof. Jean-Marie Tarascon. Publisher Copyright: {\textcopyright} 2014 Elsevier B.V. All rights reserved.",

year = "2015",

month = mar,

day = "1",

doi = "10.1016/j.jpowsour.2014.12.015",

language = "English",

volume = "277",

pages = "193--197",

journal = "Journal of Power Sources",

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Thermal stability in the blended lithium manganese oxide - Lithium nickel cobalt manganese oxide cathode materials : An in situ time-resolved X-Ray diffraction and mass spectroscopy study. / Hu, Enyuan; Bak, Seong Min; Senanayake, Sanjaya D. et al.

In: Journal of Power Sources, Vol. 277, 01.03.2015, p. 193-197.

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

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T1 - Thermal stability in the blended lithium manganese oxide - Lithium nickel cobalt manganese oxide cathode materials

T2 - An in situ time-resolved X-Ray diffraction and mass spectroscopy study

AU - Hu, Enyuan

AU - Bak, Seong Min

AU - Senanayake, Sanjaya D.

AU - Yang, Xiao Qing

AU - Nam, Kyung Wan

AU - Zhang, Lulu

AU - Shao, Minhua

N1 - Funding Information: This work was supported by the U.S. Department of Energy, the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies under Contract Number DE-AC02-98CH10886 . Use of the NSLS was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences , under Contract No. DE-AC02-98CH10886 . MS is supported by a start-up grant from the Hong Kong University of Science and Technology . This work was also supported by the Energy Efficiency & Resources of the Korea Institute of Energy Technology Evaluation and Planning grant funded by the Korea government Ministry of Trade, Industry & Energy (Project no. 20142020103090 ). The authors appreciate the invaluable discussion with Prof. Jean-Marie Tarascon. Publisher Copyright: © 2014 Elsevier B.V. All rights reserved.

PY - 2015/3/1

Y1 - 2015/3/1

N2 - Thermal stabilities of a series of blended LiMn2O4 (LMO)eLiNi1/3Co1/3Mn1/3O2 (NCM) cathode materials with different weight ratios were studied by in situ time-resolved X-ray diffraction (XRD) combined with mass spectroscopy in the temperature range of 25 °C-580 °C under helium atmosphere. Upon heating, the electrochemically delithiated LMO changed into Mn3O4 phase at around 250 °C. Formation of MnO with rock-salt structure started at 520 °C. This observation is in contrast to the previous report for chemically delithiated LMO in air, in which a process of λ-MnO2 transforming to β-MnO2 was observed. Oxygen peak was not observed in all cases, presumably as a result of either consumption by the carbon or detection limit. CO2 profile correlates well with the phase transition and indirectly suggests the oxygen release of the cathode. Introducing NCM into LMO has two effects: first, it makes the high temperature rock-salt phase formation more complicated with more peaks in CO2 profile due to different MO (M = Ni, Mn, Co) phases; secondly, the onset temperature of CO2 release is lowered, implying lowered oxygen release temperature. Upon heating, XRD patterns indicate the NCM part reacts first, followed by the LMO part. This confirms the better thermal stability of LMO over NCM.

AB - Thermal stabilities of a series of blended LiMn2O4 (LMO)eLiNi1/3Co1/3Mn1/3O2 (NCM) cathode materials with different weight ratios were studied by in situ time-resolved X-ray diffraction (XRD) combined with mass spectroscopy in the temperature range of 25 °C-580 °C under helium atmosphere. Upon heating, the electrochemically delithiated LMO changed into Mn3O4 phase at around 250 °C. Formation of MnO with rock-salt structure started at 520 °C. This observation is in contrast to the previous report for chemically delithiated LMO in air, in which a process of λ-MnO2 transforming to β-MnO2 was observed. Oxygen peak was not observed in all cases, presumably as a result of either consumption by the carbon or detection limit. CO2 profile correlates well with the phase transition and indirectly suggests the oxygen release of the cathode. Introducing NCM into LMO has two effects: first, it makes the high temperature rock-salt phase formation more complicated with more peaks in CO2 profile due to different MO (M = Ni, Mn, Co) phases; secondly, the onset temperature of CO2 release is lowered, implying lowered oxygen release temperature. Upon heating, XRD patterns indicate the NCM part reacts first, followed by the LMO part. This confirms the better thermal stability of LMO over NCM.

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Thermal stability in the blended lithium manganese oxide - Lithium nickel cobalt manganese oxide cathode materials: An in situ time-resolved X-Ray diffraction and mass spectroscopy study

Abstract

Bibliographical note

All Science Journal Classification (ASJC) codes

UN SDGs

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