Lithium diffusion coefficient in LiMn2O4 thin films measured by secondary ion mass spectrometry with ion-exchange method

Naoaki Kuwata; Masakatsu Nakane; Takamichi Miyazaki; Kazutaka Mitsuishi; Junichi Kawamura

doi:10.1016/j.ssi.2018.03.012

Lithium diffusion coefficient in LiMn₂O₄ thin films measured by secondary ion mass spectrometry with ion-exchange method

Naoaki Kuwata, Masakatsu Nakane, Takamichi Miyazaki, Kazutaka Mitsuishi, Junichi Kawamura

Division of Inorganic Material Research

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

27 Citations (Scopus)

Abstract

In this study, the lithium tracer diffusion coefficient (D_Li ^∗) in spinel-type LiMn₂O₄ thin films is measured by secondary ion mass spectroscopy (SIMS) in the temperature range from 200 to 550 °C. An ion-exchange method is employed to prepare diffusion couples consisting of the stable isotopes ⁶Li and ⁷Li. The isotope profiles were measured by SIMS analysis to determine D_Li ^∗ in the LiMn₂O₄ films. The D_Li ^∗ value was 1.4 × 10⁻¹⁰ cm²/s at 300 °C and the activation energy was 0.52 eV, which is consistent with that of bulk LiMn₂O₄. The extrapolated value of D_Li ^∗ at 25 °C was on the order of 10⁻¹⁴ cm²/s, which is smaller than the chemical diffusion coefficient of Li_xMn₂O₄ measured by electrochemical methods. The temperature dependence of D_Li ^∗ can be explained by the vacancy diffusion model, in which the extrinsic and intrinsic regions of diffusion exist in the low- and high-temperature regions, respectively.

Original language	English
Pages (from-to)	266-271
Number of pages	6
Journal	Solid State Ionics
Volume	320
DOIs	https://doi.org/10.1016/j.ssi.2018.03.012
Publication status	Published - 2018 Jul

Keywords

Lithium-ion battery
Mixed conductor
SIMS
Thin film
Tracer diffusion coefficient

ASJC Scopus subject areas

Chemistry(all)
Materials Science(all)
Condensed Matter Physics

UN SDGs

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

Access to Document

10.1016/j.ssi.2018.03.012

Cite this

@article{f6a9af02eba042b5916bccb51b700d7f,

title = "Lithium diffusion coefficient in LiMn2O4 thin films measured by secondary ion mass spectrometry with ion-exchange method",

abstract = "In this study, the lithium tracer diffusion coefficient (DLi ∗) in spinel-type LiMn2O4 thin films is measured by secondary ion mass spectroscopy (SIMS) in the temperature range from 200 to 550 °C. An ion-exchange method is employed to prepare diffusion couples consisting of the stable isotopes 6Li and 7Li. The isotope profiles were measured by SIMS analysis to determine DLi ∗ in the LiMn2O4 films. The DLi ∗ value was 1.4 × 10−10 cm2/s at 300 °C and the activation energy was 0.52 eV, which is consistent with that of bulk LiMn2O4. The extrapolated value of DLi ∗ at 25 °C was on the order of 10−14 cm2/s, which is smaller than the chemical diffusion coefficient of LixMn2O4 measured by electrochemical methods. The temperature dependence of DLi ∗ can be explained by the vacancy diffusion model, in which the extrinsic and intrinsic regions of diffusion exist in the low- and high-temperature regions, respectively.",

keywords = "Lithium-ion battery, Mixed conductor, SIMS, Thin film, Tracer diffusion coefficient",

author = "Naoaki Kuwata and Masakatsu Nakane and Takamichi Miyazaki and Kazutaka Mitsuishi and Junichi Kawamura",

note = "Funding Information: This work was supported by JSPS KAKENHI, Grant Numbers 15H03872 and 17K19134 . For the SIMS equipment, we thank the “Center for Fusion Research of Nano-Interface Devices, Tohoku University” of “Low-Carbon Research Network” funded by MEXT (Ministry of Education, Culture, Sports, Science and Technology), Japan. This study was also supported by the JST ALCA-SPRING (Specially Promoted Research for Innovative Next Generation Batteries) Project. This work was also supported by a research grant from The Murata Science Foundation ( H29助自37 ). Publisher Copyright: {\textcopyright} 2018",

year = "2018",

month = jul,

doi = "10.1016/j.ssi.2018.03.012",

language = "English",

volume = "320",

pages = "266--271",

journal = "Solid State Ionics",

issn = "0167-2738",

publisher = "Elsevier",

}

TY - JOUR

T1 - Lithium diffusion coefficient in LiMn2O4 thin films measured by secondary ion mass spectrometry with ion-exchange method

AU - Kuwata, Naoaki

AU - Nakane, Masakatsu

AU - Miyazaki, Takamichi

AU - Mitsuishi, Kazutaka

AU - Kawamura, Junichi

N1 - Funding Information: This work was supported by JSPS KAKENHI, Grant Numbers 15H03872 and 17K19134 . For the SIMS equipment, we thank the “Center for Fusion Research of Nano-Interface Devices, Tohoku University” of “Low-Carbon Research Network” funded by MEXT (Ministry of Education, Culture, Sports, Science and Technology), Japan. This study was also supported by the JST ALCA-SPRING (Specially Promoted Research for Innovative Next Generation Batteries) Project. This work was also supported by a research grant from The Murata Science Foundation ( H29助自37 ). Publisher Copyright: © 2018

PY - 2018/7

Y1 - 2018/7

N2 - In this study, the lithium tracer diffusion coefficient (DLi ∗) in spinel-type LiMn2O4 thin films is measured by secondary ion mass spectroscopy (SIMS) in the temperature range from 200 to 550 °C. An ion-exchange method is employed to prepare diffusion couples consisting of the stable isotopes 6Li and 7Li. The isotope profiles were measured by SIMS analysis to determine DLi ∗ in the LiMn2O4 films. The DLi ∗ value was 1.4 × 10−10 cm2/s at 300 °C and the activation energy was 0.52 eV, which is consistent with that of bulk LiMn2O4. The extrapolated value of DLi ∗ at 25 °C was on the order of 10−14 cm2/s, which is smaller than the chemical diffusion coefficient of LixMn2O4 measured by electrochemical methods. The temperature dependence of DLi ∗ can be explained by the vacancy diffusion model, in which the extrinsic and intrinsic regions of diffusion exist in the low- and high-temperature regions, respectively.

AB - In this study, the lithium tracer diffusion coefficient (DLi ∗) in spinel-type LiMn2O4 thin films is measured by secondary ion mass spectroscopy (SIMS) in the temperature range from 200 to 550 °C. An ion-exchange method is employed to prepare diffusion couples consisting of the stable isotopes 6Li and 7Li. The isotope profiles were measured by SIMS analysis to determine DLi ∗ in the LiMn2O4 films. The DLi ∗ value was 1.4 × 10−10 cm2/s at 300 °C and the activation energy was 0.52 eV, which is consistent with that of bulk LiMn2O4. The extrapolated value of DLi ∗ at 25 °C was on the order of 10−14 cm2/s, which is smaller than the chemical diffusion coefficient of LixMn2O4 measured by electrochemical methods. The temperature dependence of DLi ∗ can be explained by the vacancy diffusion model, in which the extrinsic and intrinsic regions of diffusion exist in the low- and high-temperature regions, respectively.

KW - Lithium-ion battery

KW - Mixed conductor

KW - SIMS

KW - Thin film

KW - Tracer diffusion coefficient

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