Intercalation of Lithium Ions from Gaseous Precursors into β-MnO 2 Thin Films Deposited by Atomic Layer Deposition

Heta-Elisa Nieminen, Ville Miikkulainen, Daniel Settipani, Laura Simonelli, Philipp Hönicke, Claudia Zech, Yves Kayser, Burkhard Beckhoff, Ari-Pekka Honkanen, Mikko J. Heikkilä, Kenichiro Mizohata, Kristoffer Meinander, Oili M.E. Ylivaara, Simo Huotari, Mikko Ritala (Corresponding Author)

    Research output: Contribution to journalArticleScientificpeer-review

    Abstract

    LiMn 2O 4 is a promising candidate for a cathode material in lithium-ion batteries because of its ability to intercalate lithium ions reversibly through its three-dimensional manganese oxide network. One of the promising techniques for depositing LiMn 2O 4 thin-film cathodes is atomic layer deposition (ALD). Because of its unparalleled film thickness control and film conformality, ALD helps to fulfill the industry demands for smaller devices, nanostructured electrodes, and all-solid-state batteries. In this work, the intercalation mechanism of Li + ions into an ALD-grown β-MnO 2 thin film was studied. Samples were prepared by pulsing LiO tBu and H 2O for different cycle numbers onto about 100 nm thick MnO 2 films at 225 °C and characterized with X-ray absorption spectroscopy, X-ray diffraction, X-ray reflectivity, time-of-flight elastic recoil detection analysis, and residual stress measurements. It is proposed that for <100 cycles of LiO tBu/H 2O, the Li + ions penetrate only to the surface region of the β-MnO 2 film, and the samples form a mixture of β-MnO 2 and a lithium-deficient nonstoichiometric spinel phase Li xMn 2O 4 (0 < x < 0.5). When the lithium concentration exceeds x ≈ 0.5 in Li xMn 2O 4 (corresponding to 100 cycles of LiO tBu/H 2O), the crystalline phase of manganese oxide changes from the tetragonal pyrolusite to the cubic spinel, which enables the Li + ions to migrate throughout the whole film. Annealing in N 2 at 600 °C after the lithium incorporation seemed to convert the films completely to the pure cubic spinel LiMn 2O 4.

    Original languageEnglish
    Pages (from-to)15802-15814
    Number of pages13
    JournalJournal of Physical Chemistry C
    Volume123
    Issue number25
    DOIs
    Publication statusPublished - 27 Jun 2019
    MoE publication typeA1 Journal article-refereed

    Fingerprint

    Atomic layer deposition
    Intercalation
    atomic layer epitaxy
    Lithium
    intercalation
    lithium
    Ions
    Thin films
    spinel
    thin films
    Manganese oxide
    manganese oxides
    ions
    cycles
    electric batteries
    Cathodes
    cathodes
    Thickness control
    X ray absorption spectroscopy
    x rays

    Cite this

    Nieminen, H-E., Miikkulainen, V., Settipani, D., Simonelli, L., Hönicke, P., Zech, C., ... Ritala, M. (2019). Intercalation of Lithium Ions from Gaseous Precursors into β-MnO 2 Thin Films Deposited by Atomic Layer Deposition. Journal of Physical Chemistry C, 123(25), 15802-15814. https://doi.org/10.1021/acs.jpcc.9b03039
    Nieminen, Heta-Elisa ; Miikkulainen, Ville ; Settipani, Daniel ; Simonelli, Laura ; Hönicke, Philipp ; Zech, Claudia ; Kayser, Yves ; Beckhoff, Burkhard ; Honkanen, Ari-Pekka ; Heikkilä, Mikko J. ; Mizohata, Kenichiro ; Meinander, Kristoffer ; Ylivaara, Oili M.E. ; Huotari, Simo ; Ritala, Mikko. / Intercalation of Lithium Ions from Gaseous Precursors into β-MnO 2 Thin Films Deposited by Atomic Layer Deposition. In: Journal of Physical Chemistry C. 2019 ; Vol. 123, No. 25. pp. 15802-15814.
    @article{1b611ee1e89f45eea720dbe4a7569b8d,
    title = "Intercalation of Lithium Ions from Gaseous Precursors into β-MnO 2 Thin Films Deposited by Atomic Layer Deposition",
    abstract = "LiMn 2O 4 is a promising candidate for a cathode material in lithium-ion batteries because of its ability to intercalate lithium ions reversibly through its three-dimensional manganese oxide network. One of the promising techniques for depositing LiMn 2O 4 thin-film cathodes is atomic layer deposition (ALD). Because of its unparalleled film thickness control and film conformality, ALD helps to fulfill the industry demands for smaller devices, nanostructured electrodes, and all-solid-state batteries. In this work, the intercalation mechanism of Li + ions into an ALD-grown β-MnO 2 thin film was studied. Samples were prepared by pulsing LiO tBu and H 2O for different cycle numbers onto about 100 nm thick MnO 2 films at 225 °C and characterized with X-ray absorption spectroscopy, X-ray diffraction, X-ray reflectivity, time-of-flight elastic recoil detection analysis, and residual stress measurements. It is proposed that for <100 cycles of LiO tBu/H 2O, the Li + ions penetrate only to the surface region of the β-MnO 2 film, and the samples form a mixture of β-MnO 2 and a lithium-deficient nonstoichiometric spinel phase Li xMn 2O 4 (0 < x < 0.5). When the lithium concentration exceeds x ≈ 0.5 in Li xMn 2O 4 (corresponding to 100 cycles of LiO tBu/H 2O), the crystalline phase of manganese oxide changes from the tetragonal pyrolusite to the cubic spinel, which enables the Li + ions to migrate throughout the whole film. Annealing in N 2 at 600 °C after the lithium incorporation seemed to convert the films completely to the pure cubic spinel LiMn 2O 4.",
    author = "Heta-Elisa Nieminen and Ville Miikkulainen and Daniel Settipani and Laura Simonelli and Philipp H{\"o}nicke and Claudia Zech and Yves Kayser and Burkhard Beckhoff and Ari-Pekka Honkanen and Heikkil{\"a}, {Mikko J.} and Kenichiro Mizohata and Kristoffer Meinander and Ylivaara, {Oili M.E.} and Simo Huotari and Mikko Ritala",
    year = "2019",
    month = "6",
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    doi = "10.1021/acs.jpcc.9b03039",
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    Nieminen, H-E, Miikkulainen, V, Settipani, D, Simonelli, L, Hönicke, P, Zech, C, Kayser, Y, Beckhoff, B, Honkanen, A-P, Heikkilä, MJ, Mizohata, K, Meinander, K, Ylivaara, OME, Huotari, S & Ritala, M 2019, 'Intercalation of Lithium Ions from Gaseous Precursors into β-MnO 2 Thin Films Deposited by Atomic Layer Deposition', Journal of Physical Chemistry C, vol. 123, no. 25, pp. 15802-15814. https://doi.org/10.1021/acs.jpcc.9b03039

    Intercalation of Lithium Ions from Gaseous Precursors into β-MnO 2 Thin Films Deposited by Atomic Layer Deposition. / Nieminen, Heta-Elisa ; Miikkulainen, Ville; Settipani, Daniel ; Simonelli, Laura; Hönicke, Philipp ; Zech, Claudia; Kayser, Yves; Beckhoff, Burkhard; Honkanen, Ari-Pekka; Heikkilä, Mikko J.; Mizohata, Kenichiro; Meinander, Kristoffer; Ylivaara, Oili M.E.; Huotari, Simo; Ritala, Mikko (Corresponding Author).

    In: Journal of Physical Chemistry C, Vol. 123, No. 25, 27.06.2019, p. 15802-15814.

    Research output: Contribution to journalArticleScientificpeer-review

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    T1 - Intercalation of Lithium Ions from Gaseous Precursors into β-MnO 2 Thin Films Deposited by Atomic Layer Deposition

    AU - Nieminen, Heta-Elisa

    AU - Miikkulainen, Ville

    AU - Settipani, Daniel

    AU - Simonelli, Laura

    AU - Hönicke, Philipp

    AU - Zech, Claudia

    AU - Kayser, Yves

    AU - Beckhoff, Burkhard

    AU - Honkanen, Ari-Pekka

    AU - Heikkilä, Mikko J.

    AU - Mizohata, Kenichiro

    AU - Meinander, Kristoffer

    AU - Ylivaara, Oili M.E.

    AU - Huotari, Simo

    AU - Ritala, Mikko

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    Y1 - 2019/6/27

    N2 - LiMn 2O 4 is a promising candidate for a cathode material in lithium-ion batteries because of its ability to intercalate lithium ions reversibly through its three-dimensional manganese oxide network. One of the promising techniques for depositing LiMn 2O 4 thin-film cathodes is atomic layer deposition (ALD). Because of its unparalleled film thickness control and film conformality, ALD helps to fulfill the industry demands for smaller devices, nanostructured electrodes, and all-solid-state batteries. In this work, the intercalation mechanism of Li + ions into an ALD-grown β-MnO 2 thin film was studied. Samples were prepared by pulsing LiO tBu and H 2O for different cycle numbers onto about 100 nm thick MnO 2 films at 225 °C and characterized with X-ray absorption spectroscopy, X-ray diffraction, X-ray reflectivity, time-of-flight elastic recoil detection analysis, and residual stress measurements. It is proposed that for <100 cycles of LiO tBu/H 2O, the Li + ions penetrate only to the surface region of the β-MnO 2 film, and the samples form a mixture of β-MnO 2 and a lithium-deficient nonstoichiometric spinel phase Li xMn 2O 4 (0 < x < 0.5). When the lithium concentration exceeds x ≈ 0.5 in Li xMn 2O 4 (corresponding to 100 cycles of LiO tBu/H 2O), the crystalline phase of manganese oxide changes from the tetragonal pyrolusite to the cubic spinel, which enables the Li + ions to migrate throughout the whole film. Annealing in N 2 at 600 °C after the lithium incorporation seemed to convert the films completely to the pure cubic spinel LiMn 2O 4.

    AB - LiMn 2O 4 is a promising candidate for a cathode material in lithium-ion batteries because of its ability to intercalate lithium ions reversibly through its three-dimensional manganese oxide network. One of the promising techniques for depositing LiMn 2O 4 thin-film cathodes is atomic layer deposition (ALD). Because of its unparalleled film thickness control and film conformality, ALD helps to fulfill the industry demands for smaller devices, nanostructured electrodes, and all-solid-state batteries. In this work, the intercalation mechanism of Li + ions into an ALD-grown β-MnO 2 thin film was studied. Samples were prepared by pulsing LiO tBu and H 2O for different cycle numbers onto about 100 nm thick MnO 2 films at 225 °C and characterized with X-ray absorption spectroscopy, X-ray diffraction, X-ray reflectivity, time-of-flight elastic recoil detection analysis, and residual stress measurements. It is proposed that for <100 cycles of LiO tBu/H 2O, the Li + ions penetrate only to the surface region of the β-MnO 2 film, and the samples form a mixture of β-MnO 2 and a lithium-deficient nonstoichiometric spinel phase Li xMn 2O 4 (0 < x < 0.5). When the lithium concentration exceeds x ≈ 0.5 in Li xMn 2O 4 (corresponding to 100 cycles of LiO tBu/H 2O), the crystalline phase of manganese oxide changes from the tetragonal pyrolusite to the cubic spinel, which enables the Li + ions to migrate throughout the whole film. Annealing in N 2 at 600 °C after the lithium incorporation seemed to convert the films completely to the pure cubic spinel LiMn 2O 4.

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    JF - Journal of Physical Chemistry C

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