Impact of thermal gas treatment on the surface modification of Li-rich Mn-based cathode materials for Li-ion batteries

Maximilian Mellin; Zhili Liang; Hadar Sclar; Sandipan Maiti; Igor Píš; Silvia Nappini; Elena Magnano; Federica Bondino; Ilargi Napal; Robert Winkler; Réne Hausbrand; Jan P. Hofmann; Lambert Alff; Boris Markovsky; Doron Aurbach; Wolfram Jaegermann; Gennady Cherkashinin

doi:10.1039/d3ma00236e

Impact of thermal gas treatment on the surface modification of Li-rich Mn-based cathode materials for Li-ion batteries

Maximilian Mellin, Zhili Liang, Hadar Sclar, Sandipan Maiti, Igor Píš, Silvia Nappini, Elena Magnano, Federica Bondino, Ilargi Napal, Robert Winkler, Réne Hausbrand, Jan P. Hofmann, Lambert Alff, Boris Markovsky, Doron Aurbach, Wolfram Jaegermann, Gennady Cherkashinin

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

2 Scopus citations

Abstract

High energy density Li-rich 0.33Li₂MnO₃·0.67LiNi_0.4Co_0.2Mn_0.4O₂ (HE-NCM) layered structure cathodes for Li-ion batteries provide higher capacity gain via incorporation of an excess of lithium into the host. As a serious drawback, these cathodes suffer from continuous voltage fade upon cycling. Recently, high capacity retention, rate capability and low voltage hysteresis were achieved for HE-NCM by new thermal double gases SO₂ and NH₃ treatment. However, so far a fundamental understanding of the mechanisms responsible for this improved stability is missing. Herein, a comprehensive study of the chemical composition and electronic structure modifications of a series of HE-NCM (untreated, treated, carbon- and binder- free) is performed using advanced electron spectroscopy techniques supported by theoretical calculations. We demonstrate that the double gases treatment process leads to a partial reduction of Co³⁺ and Mn⁴⁺. The suggested chemical reactions include electron transfer from SO₂, which behaves as a Lewis acid, to the transition metal sites accompanied by decomposition of SO₂ and a characteristic surface modification which acts as protective layer for the HE-NCM.

Original language	English
Pages (from-to)	3746-3758
Number of pages	13
Journal	Materials Advances
Volume	4
Issue number	17
DOIs	https://doi.org/10.1039/d3ma00236e
State	Published - 24 Jul 2023

Bibliographical note

Publisher Copyright:
© 2023 RSC.

Funding

This work was supported by the German Science Foundation (DFG, project numbers 416542991 and HA 6128/6-1). A part of the work was performed within DFG, CH566/4-1 project. The authors acknowledge Elettra Sincrotrone Trieste and IOM-CNR (Trieste, Italy) and Diamond Light Source (Oxford, UK) for providing access to synchrotron radiation facilities and for financial support (the project no. SI31579-1). The authors thank Pardeep Kumar and Tien-Lin Lee for their support during the synchrotron measurements at the I09 beamline. In addition, the authors thank Boburmirzo Juraev and Michael Walter for their involvement in the XPS measurements during their advanced research laboratory (ARL) work at TU Darmstadt. Research at IOM-CNR has been funded by the European Union - NextGenerationEU under the Italian Ministry of University and Research (MUR) National Innovation Ecosystem grant ECS00000041 - VITALITY. F. B. acknowledges Università degli Studi di Perugia and MUR, CNR for support within the project Vitality. I. P., S. N., E. M., and F. B. acknowledge funding from the EUROFEL project (RoadMap Esfri).

Funders	Funder number
IOM-CNR
Diamond Light Source	SI31579-1
Elettra-Sincrotrone Trieste
European Commission
Deutsche Forschungsgemeinschaft	416542991, HA 6128/6-1
Ministero dell’Istruzione, dell’Università e della Ricerca	ECS00000041 - VITALITY
Consiglio Nazionale delle Ricerche
Technische Universität Darmstadt
Università degli Studi di Perugia

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10.1039/d3ma00236e

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Mellin, M., Liang, Z., Sclar, H., Maiti, S., Píš, I., Nappini, S., Magnano, E., Bondino, F., Napal, I., Winkler, R., Hausbrand, R., Hofmann, J. P., Alff, L., Markovsky, B., Aurbach, D., Jaegermann, W., & Cherkashinin, G. (2023). Impact of thermal gas treatment on the surface modification of Li-rich Mn-based cathode materials for Li-ion batteries. Materials Advances, 4(17), 3746-3758. https://doi.org/10.1039/d3ma00236e

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title = "Impact of thermal gas treatment on the surface modification of Li-rich Mn-based cathode materials for Li-ion batteries",

abstract = "High energy density Li-rich 0.33Li2MnO3·0.67LiNi0.4Co0.2Mn0.4O2 (HE-NCM) layered structure cathodes for Li-ion batteries provide higher capacity gain via incorporation of an excess of lithium into the host. As a serious drawback, these cathodes suffer from continuous voltage fade upon cycling. Recently, high capacity retention, rate capability and low voltage hysteresis were achieved for HE-NCM by new thermal double gases SO2 and NH3 treatment. However, so far a fundamental understanding of the mechanisms responsible for this improved stability is missing. Herein, a comprehensive study of the chemical composition and electronic structure modifications of a series of HE-NCM (untreated, treated, carbon- and binder- free) is performed using advanced electron spectroscopy techniques supported by theoretical calculations. We demonstrate that the double gases treatment process leads to a partial reduction of Co3+ and Mn4+. The suggested chemical reactions include electron transfer from SO2, which behaves as a Lewis acid, to the transition metal sites accompanied by decomposition of SO2 and a characteristic surface modification which acts as protective layer for the HE-NCM.",

author = "Maximilian Mellin and Zhili Liang and Hadar Sclar and Sandipan Maiti and Igor P{\'i}{\v s} and Silvia Nappini and Elena Magnano and Federica Bondino and Ilargi Napal and Robert Winkler and R{\'e}ne Hausbrand and Hofmann, {Jan P.} and Lambert Alff and Boris Markovsky and Doron Aurbach and Wolfram Jaegermann and Gennady Cherkashinin",

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year = "2023",

month = jul,

day = "24",

doi = "10.1039/d3ma00236e",

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Mellin, M, Liang, Z, Sclar, H, Maiti, S, Píš, I, Nappini, S, Magnano, E, Bondino, F, Napal, I, Winkler, R, Hausbrand, R, Hofmann, JP, Alff, L, Markovsky, B, Aurbach, D, Jaegermann, W & Cherkashinin, G 2023, 'Impact of thermal gas treatment on the surface modification of Li-rich Mn-based cathode materials for Li-ion batteries', Materials Advances, vol. 4, no. 17, pp. 3746-3758. https://doi.org/10.1039/d3ma00236e

TY - JOUR

T1 - Impact of thermal gas treatment on the surface modification of Li-rich Mn-based cathode materials for Li-ion batteries

AU - Mellin, Maximilian

AU - Liang, Zhili

AU - Sclar, Hadar

AU - Maiti, Sandipan

AU - Píš, Igor

AU - Nappini, Silvia

AU - Magnano, Elena

AU - Bondino, Federica

AU - Napal, Ilargi

AU - Winkler, Robert

AU - Hausbrand, Réne

AU - Hofmann, Jan P.

AU - Alff, Lambert

AU - Markovsky, Boris

AU - Aurbach, Doron

AU - Jaegermann, Wolfram

AU - Cherkashinin, Gennady

PY - 2023/7/24

Y1 - 2023/7/24

N2 - High energy density Li-rich 0.33Li2MnO3·0.67LiNi0.4Co0.2Mn0.4O2 (HE-NCM) layered structure cathodes for Li-ion batteries provide higher capacity gain via incorporation of an excess of lithium into the host. As a serious drawback, these cathodes suffer from continuous voltage fade upon cycling. Recently, high capacity retention, rate capability and low voltage hysteresis were achieved for HE-NCM by new thermal double gases SO2 and NH3 treatment. However, so far a fundamental understanding of the mechanisms responsible for this improved stability is missing. Herein, a comprehensive study of the chemical composition and electronic structure modifications of a series of HE-NCM (untreated, treated, carbon- and binder- free) is performed using advanced electron spectroscopy techniques supported by theoretical calculations. We demonstrate that the double gases treatment process leads to a partial reduction of Co3+ and Mn4+. The suggested chemical reactions include electron transfer from SO2, which behaves as a Lewis acid, to the transition metal sites accompanied by decomposition of SO2 and a characteristic surface modification which acts as protective layer for the HE-NCM.

AB - High energy density Li-rich 0.33Li2MnO3·0.67LiNi0.4Co0.2Mn0.4O2 (HE-NCM) layered structure cathodes for Li-ion batteries provide higher capacity gain via incorporation of an excess of lithium into the host. As a serious drawback, these cathodes suffer from continuous voltage fade upon cycling. Recently, high capacity retention, rate capability and low voltage hysteresis were achieved for HE-NCM by new thermal double gases SO2 and NH3 treatment. However, so far a fundamental understanding of the mechanisms responsible for this improved stability is missing. Herein, a comprehensive study of the chemical composition and electronic structure modifications of a series of HE-NCM (untreated, treated, carbon- and binder- free) is performed using advanced electron spectroscopy techniques supported by theoretical calculations. We demonstrate that the double gases treatment process leads to a partial reduction of Co3+ and Mn4+. The suggested chemical reactions include electron transfer from SO2, which behaves as a Lewis acid, to the transition metal sites accompanied by decomposition of SO2 and a characteristic surface modification which acts as protective layer for the HE-NCM.

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SN - 2633-5409

VL - 4

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JO - Materials Advances

JF - Materials Advances

IS - 17

ER -

Impact of thermal gas treatment on the surface modification of Li-rich Mn-based cathode materials for Li-ion batteries

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