Operando Observations and First-Principles Calculations of Reduced Lithium Insertion in Au-Coated LiMn                         2                         O                         4

Kimberly L. Bassett; Robert E. Warburton; Siddharth Deshpande; Timothy T. Fister; Kim Ta; Jennifer L. Esbenshade; Alper Kinaci; Maria K.Y. Chan; Kamila M. Wiaderek; Karena W. Chapman; Jeffrey P. Greeley; Andrew A. Gewirth

doi:10.1002/admi.201801923

Operando Observations and First-Principles Calculations of Reduced Lithium Insertion in Au-Coated LiMn ₂ O ₄

Kimberly L. Bassett, Robert E. Warburton, Siddharth Deshpande, Timothy T. Fister, Kim Ta, Jennifer L. Esbenshade, Alper Kinaci, Maria K.Y. Chan, Kamila M. Wiaderek, Karena W. Chapman, Jeffrey P. Greeley^*, Andrew A. Gewirth

^*Corresponding author for this work

MRC - Materials Research Center

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

14 Scopus citations

Abstract

The deposition of protective coatings on the spinel LiMn ₂ O ₄ (LMO) lithium-ion battery cathode is effective in reducing Mn dissolution from the electrode surface. Although protective coatings positively affect LMO cycle life, much remains to be understood regarding the interface formed between these coatings and LMO. Using operando powder X-ray diffraction with Rietveld refinement, it is shown that, in comparison to bare LMO, the lattice parameter of a model Au-coated LMO cathode is significantly reduced upon relithiation. Less charge passes through Au-coated LMO in comparison to bare LMO, suggesting that the reduced lattice parameter is associated with decreased Li ⁺ solubility in the Au-coated LMO. Density functional theory calculations show that a more Li ⁺ -deficient near-surface is thermodynamically favorable in the presence of the Au coating, which may further stabilize these cathodes through suppressing formation of the Jahn–Teller distorted Li ₂ Mn ₂ O ₄ phase at the surface. Electronic structure and chemical bonding analyses show enhanced hybridization between Au and LMO for delithiated surfaces leading to partial oxidation of Au upon delithiation. This study suggests that, in addition to transition metal dissolution from electrode surfaces, protective coating design must also balance potential energy effects induced by charge transfer at the electrode-coating interface.

Original language	English (US)
Article number	1801923
Journal	Advanced Materials Interfaces
Volume	6
Issue number	4
DOIs	https://doi.org/10.1002/admi.201801923
State	Published - Feb 22 2019

Funding

K.L.B. and R.E.W. contributed equally to this work. This research was supported as part of the Center for Electrochemical Energy Science, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, and Basic Energy Sciences (BES). Use of the Center for Nanoscale Materials was supported by the U.S. Department of Energy, Office of Science, and Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. This research used resources of the National Energy Research Scientific Computing Center and a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. 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. The authors thank Wenqian Xu at the Advanced Photon Source 17-BM Beamline for his advice and thoughtful comments. K.L.B. acknowledges support from the National Science Foundation Graduate Research Fellowship Program under Grant No. DGE-1144245. K.L.B. and R.E.W. contributed equally to this work. This research was supported as part of the Center for Electrochemical Energy Science, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, and Basic Energy Sciences (BES). Use of the Center for Nanoscale Materials was supported by the U.S. Department of Energy, Office of Science, and Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. This research used resources of the National Energy Research Scientific Computing Center and a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. 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. The authors thank Wenqian Xu at the Advanced Photon Source 17-BM Beamline for his advice and thoughtful comments. K.L.B. acknowledges support from the National Science Foundation Graduate Research Fellowship Program under Grant No. DGE-1144245.

Keywords

density functional theory
lithium manganese oxide
lithium-ion batteries
operando X-ray diffraction
protective coatings

ASJC Scopus subject areas

Mechanics of Materials
Mechanical Engineering

UN SDGs

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

Access to Document

10.1002/admi.201801923

Cite this

Bassett, K. L., Warburton, R. E., Deshpande, S., Fister, T. T., Ta, K., Esbenshade, J. L., Kinaci, A., Chan, M. K. Y., Wiaderek, K. M., Chapman, K. W., Greeley, J. P., & Gewirth, A. A. (2019). Operando Observations and First-Principles Calculations of Reduced Lithium Insertion in Au-Coated LiMn ₂ O ₄. Advanced Materials Interfaces, 6(4), Article 1801923. https://doi.org/10.1002/admi.201801923

@article{abca25bf41814fae8eb6d0f6c79f4bf8,

title = "Operando Observations and First-Principles Calculations of Reduced Lithium Insertion in Au-Coated LiMn 2 O 4",

abstract = " The deposition of protective coatings on the spinel LiMn 2 O 4 (LMO) lithium-ion battery cathode is effective in reducing Mn dissolution from the electrode surface. Although protective coatings positively affect LMO cycle life, much remains to be understood regarding the interface formed between these coatings and LMO. Using operando powder X-ray diffraction with Rietveld refinement, it is shown that, in comparison to bare LMO, the lattice parameter of a model Au-coated LMO cathode is significantly reduced upon relithiation. Less charge passes through Au-coated LMO in comparison to bare LMO, suggesting that the reduced lattice parameter is associated with decreased Li + solubility in the Au-coated LMO. Density functional theory calculations show that a more Li + -deficient near-surface is thermodynamically favorable in the presence of the Au coating, which may further stabilize these cathodes through suppressing formation of the Jahn–Teller distorted Li 2 Mn 2 O 4 phase at the surface. Electronic structure and chemical bonding analyses show enhanced hybridization between Au and LMO for delithiated surfaces leading to partial oxidation of Au upon delithiation. This study suggests that, in addition to transition metal dissolution from electrode surfaces, protective coating design must also balance potential energy effects induced by charge transfer at the electrode-coating interface.",

keywords = "density functional theory, lithium manganese oxide, lithium-ion batteries, operando X-ray diffraction, protective coatings",

author = "Bassett, {Kimberly L.} and Warburton, {Robert E.} and Siddharth Deshpande and Fister, {Timothy T.} and Kim Ta and Esbenshade, {Jennifer L.} and Alper Kinaci and Chan, {Maria K.Y.} and Wiaderek, {Kamila M.} and Chapman, {Karena W.} and Greeley, {Jeffrey P.} and Gewirth, {Andrew A.}",

note = "Funding Information: K.L.B. and R.E.W. contributed equally to this work. This research was supported as part of the Center for Electrochemical Energy Science, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, and Basic Energy Sciences (BES). Use of the Center for Nanoscale Materials was supported by the U.S. Department of Energy, Office of Science, and Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. This research used resources of the National Energy Research Scientific Computing Center and a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. 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. The authors thank Wenqian Xu at the Advanced Photon Source 17-BM Beamline for his advice and thoughtful comments. K.L.B. acknowledges support from the National Science Foundation Graduate Research Fellowship Program under Grant No. DGE-1144245. Funding Information: K.L.B. and R.E.W. contributed equally to this work. This research was supported as part of the Center for Electrochemical Energy Science, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, and Basic Energy Sciences (BES). Use of the Center for Nanoscale Materials was supported by the U.S. Department of Energy, Office of Science, and Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. This research used resources of the National Energy Research Scientific Computing Center and a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. 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. The authors thank Wenqian Xu at the Advanced Photon Source 17-BM Beamline for his advice and thoughtful comments. K.L.B. acknowledges support from the National Science Foundation Graduate Research Fellowship Program under Grant No. DGE-1144245. Publisher Copyright: {\textcopyright} 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2019",

month = feb,

day = "22",

doi = "10.1002/admi.201801923",

language = "English (US)",

volume = "6",

journal = "Advanced Materials Interfaces",

issn = "2196-7350",

publisher = "John Wiley and Sons Ltd",

number = "4",

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Bassett, KL, Warburton, RE, Deshpande, S, Fister, TT, Ta, K, Esbenshade, JL, Kinaci, A, Chan, MKY, Wiaderek, KM, Chapman, KW, Greeley, JP & Gewirth, AA 2019, 'Operando Observations and First-Principles Calculations of Reduced Lithium Insertion in Au-Coated LiMn ₂ O ₄', Advanced Materials Interfaces, vol. 6, no. 4, 1801923. https://doi.org/10.1002/admi.201801923

Operando Observations and First-Principles Calculations of Reduced Lithium Insertion in Au-Coated LiMn ₂ O ₄. / Bassett, Kimberly L.; Warburton, Robert E.; Deshpande, Siddharth et al.
In: Advanced Materials Interfaces, Vol. 6, No. 4, 1801923, 22.02.2019.

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

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T1 - Operando Observations and First-Principles Calculations of Reduced Lithium Insertion in Au-Coated LiMn 2 O 4

AU - Bassett, Kimberly L.

AU - Warburton, Robert E.

AU - Deshpande, Siddharth

AU - Fister, Timothy T.

AU - Ta, Kim

AU - Esbenshade, Jennifer L.

AU - Kinaci, Alper

AU - Chan, Maria K.Y.

AU - Wiaderek, Kamila M.

AU - Chapman, Karena W.

AU - Greeley, Jeffrey P.

AU - Gewirth, Andrew A.

N1 - Funding Information: K.L.B. and R.E.W. contributed equally to this work. This research was supported as part of the Center for Electrochemical Energy Science, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, and Basic Energy Sciences (BES). Use of the Center for Nanoscale Materials was supported by the U.S. Department of Energy, Office of Science, and Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. This research used resources of the National Energy Research Scientific Computing Center and a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. 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. The authors thank Wenqian Xu at the Advanced Photon Source 17-BM Beamline for his advice and thoughtful comments. K.L.B. acknowledges support from the National Science Foundation Graduate Research Fellowship Program under Grant No. DGE-1144245. Funding Information: K.L.B. and R.E.W. contributed equally to this work. This research was supported as part of the Center for Electrochemical Energy Science, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, and Basic Energy Sciences (BES). Use of the Center for Nanoscale Materials was supported by the U.S. Department of Energy, Office of Science, and Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. This research used resources of the National Energy Research Scientific Computing Center and a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. 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. The authors thank Wenqian Xu at the Advanced Photon Source 17-BM Beamline for his advice and thoughtful comments. K.L.B. acknowledges support from the National Science Foundation Graduate Research Fellowship Program under Grant No. DGE-1144245. Publisher Copyright: © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2019/2/22

Y1 - 2019/2/22

N2 - The deposition of protective coatings on the spinel LiMn 2 O 4 (LMO) lithium-ion battery cathode is effective in reducing Mn dissolution from the electrode surface. Although protective coatings positively affect LMO cycle life, much remains to be understood regarding the interface formed between these coatings and LMO. Using operando powder X-ray diffraction with Rietveld refinement, it is shown that, in comparison to bare LMO, the lattice parameter of a model Au-coated LMO cathode is significantly reduced upon relithiation. Less charge passes through Au-coated LMO in comparison to bare LMO, suggesting that the reduced lattice parameter is associated with decreased Li + solubility in the Au-coated LMO. Density functional theory calculations show that a more Li + -deficient near-surface is thermodynamically favorable in the presence of the Au coating, which may further stabilize these cathodes through suppressing formation of the Jahn–Teller distorted Li 2 Mn 2 O 4 phase at the surface. Electronic structure and chemical bonding analyses show enhanced hybridization between Au and LMO for delithiated surfaces leading to partial oxidation of Au upon delithiation. This study suggests that, in addition to transition metal dissolution from electrode surfaces, protective coating design must also balance potential energy effects induced by charge transfer at the electrode-coating interface.

AB - The deposition of protective coatings on the spinel LiMn 2 O 4 (LMO) lithium-ion battery cathode is effective in reducing Mn dissolution from the electrode surface. Although protective coatings positively affect LMO cycle life, much remains to be understood regarding the interface formed between these coatings and LMO. Using operando powder X-ray diffraction with Rietveld refinement, it is shown that, in comparison to bare LMO, the lattice parameter of a model Au-coated LMO cathode is significantly reduced upon relithiation. Less charge passes through Au-coated LMO in comparison to bare LMO, suggesting that the reduced lattice parameter is associated with decreased Li + solubility in the Au-coated LMO. Density functional theory calculations show that a more Li + -deficient near-surface is thermodynamically favorable in the presence of the Au coating, which may further stabilize these cathodes through suppressing formation of the Jahn–Teller distorted Li 2 Mn 2 O 4 phase at the surface. Electronic structure and chemical bonding analyses show enhanced hybridization between Au and LMO for delithiated surfaces leading to partial oxidation of Au upon delithiation. This study suggests that, in addition to transition metal dissolution from electrode surfaces, protective coating design must also balance potential energy effects induced by charge transfer at the electrode-coating interface.

KW - density functional theory

KW - lithium manganese oxide

KW - lithium-ion batteries

KW - operando X-ray diffraction

KW - protective coatings

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