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.
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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",
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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

PY - 2019/6/27

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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