Kinetically asymmetric charge and discharge behavior of LiNi 0.5Mn1.5O4 at low temperature observed by in situ X-ray diffraction

Ikuma Takahashi, Haruno Murayama, Kenji Sato, Takahiro Naka, Koji Kitada, Katsutoshi Fukuda, Yukinori Koyama, Hajime Arai, Eiichiro Matsubara, Yoshiharu Uchimoto, Zempachi Ogumi

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

Capacity decrease at low temperatures is one of the issues to be solved for secondary batteries especially for automobile applications and it is thus important to clarify the reaction kinetics in operating batteries and identify the rate determining step that governs the performance at low temperatures. Phase transitions in electrode active materials are important factors that affect the reaction kinetics particularly for thin electrodes used in high power applications. In this study, the phase transition dynamics of thin LiNi 0.5Mn1.5O4 electrodes at various temperatures is examined using electrochemical methods combined with temperature-controlled in situ X-ray diffraction analysis to directly capture the reacting species and elucidate the reaction mechanism. The analysis shows that there occur consecutive phase transitions of LiNi0.5Mn1.5O4 (Li1 phase) ↔ Li0.5Ni0.5Mn1.5O 4 (Li0.5 phase) and the Li0.5 phase ↔ Ni0.5Mn 1.5O4 (Li0 phase) at room temperature and above. At lower temperatures the transition of Li1 → Li0.5 proceeds during the charging process but further delithiation to form the Li0 phase is restricted, leading to the capacity decrease. On the other hand, on discharging at low temperatures the amount of the Li0 phase to be lithiated is limited and this causes the capacity decrease. There is no Li0.5 phase formation on discharging at low temperatures, revealing remarkable kinetic asymmetry of the reaction processes for charging and discharging. It is suggested that the Li0.5 phase formed on discharging is instantly lithiated to form the Li1 phase, due to the small potential gap between the two transitions. These results indicate that the phase transition kinetics of Li0.5 ↔ Li0 is slower than that of Li1 ↔ Li0.5 and the former transition is the rate determining step at low temperatures.

Original languageEnglish
Pages (from-to)15414-15419
Number of pages6
JournalJournal of Materials Chemistry A
Volume2
Issue number37
DOIs
Publication statusPublished - Oct 7 2014

Fingerprint

X ray diffraction
Phase transitions
Temperature
Reaction kinetics
Electrodes
Kinetics
Secondary batteries
X ray diffraction analysis
Automobiles

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Renewable Energy, Sustainability and the Environment
  • Materials Science(all)

Cite this

Kinetically asymmetric charge and discharge behavior of LiNi 0.5Mn1.5O4 at low temperature observed by in situ X-ray diffraction. / Takahashi, Ikuma; Murayama, Haruno; Sato, Kenji; Naka, Takahiro; Kitada, Koji; Fukuda, Katsutoshi; Koyama, Yukinori; Arai, Hajime; Matsubara, Eiichiro; Uchimoto, Yoshiharu; Ogumi, Zempachi.

In: Journal of Materials Chemistry A, Vol. 2, No. 37, 07.10.2014, p. 15414-15419.

Research output: Contribution to journalArticle

Takahashi, I, Murayama, H, Sato, K, Naka, T, Kitada, K, Fukuda, K, Koyama, Y, Arai, H, Matsubara, E, Uchimoto, Y & Ogumi, Z 2014, 'Kinetically asymmetric charge and discharge behavior of LiNi 0.5Mn1.5O4 at low temperature observed by in situ X-ray diffraction', Journal of Materials Chemistry A, vol. 2, no. 37, pp. 15414-15419. https://doi.org/10.1039/c4ta01130a
Takahashi, Ikuma ; Murayama, Haruno ; Sato, Kenji ; Naka, Takahiro ; Kitada, Koji ; Fukuda, Katsutoshi ; Koyama, Yukinori ; Arai, Hajime ; Matsubara, Eiichiro ; Uchimoto, Yoshiharu ; Ogumi, Zempachi. / Kinetically asymmetric charge and discharge behavior of LiNi 0.5Mn1.5O4 at low temperature observed by in situ X-ray diffraction. In: Journal of Materials Chemistry A. 2014 ; Vol. 2, No. 37. pp. 15414-15419.
@article{b2d603958a2f45d5ba446ca3175b1eec,
title = "Kinetically asymmetric charge and discharge behavior of LiNi 0.5Mn1.5O4 at low temperature observed by in situ X-ray diffraction",
abstract = "Capacity decrease at low temperatures is one of the issues to be solved for secondary batteries especially for automobile applications and it is thus important to clarify the reaction kinetics in operating batteries and identify the rate determining step that governs the performance at low temperatures. Phase transitions in electrode active materials are important factors that affect the reaction kinetics particularly for thin electrodes used in high power applications. In this study, the phase transition dynamics of thin LiNi 0.5Mn1.5O4 electrodes at various temperatures is examined using electrochemical methods combined with temperature-controlled in situ X-ray diffraction analysis to directly capture the reacting species and elucidate the reaction mechanism. The analysis shows that there occur consecutive phase transitions of LiNi0.5Mn1.5O4 (Li1 phase) ↔ Li0.5Ni0.5Mn1.5O 4 (Li0.5 phase) and the Li0.5 phase ↔ Ni0.5Mn 1.5O4 (Li0 phase) at room temperature and above. At lower temperatures the transition of Li1 → Li0.5 proceeds during the charging process but further delithiation to form the Li0 phase is restricted, leading to the capacity decrease. On the other hand, on discharging at low temperatures the amount of the Li0 phase to be lithiated is limited and this causes the capacity decrease. There is no Li0.5 phase formation on discharging at low temperatures, revealing remarkable kinetic asymmetry of the reaction processes for charging and discharging. It is suggested that the Li0.5 phase formed on discharging is instantly lithiated to form the Li1 phase, due to the small potential gap between the two transitions. These results indicate that the phase transition kinetics of Li0.5 ↔ Li0 is slower than that of Li1 ↔ Li0.5 and the former transition is the rate determining step at low temperatures.",
author = "Ikuma Takahashi and Haruno Murayama and Kenji Sato and Takahiro Naka and Koji Kitada and Katsutoshi Fukuda and Yukinori Koyama and Hajime Arai and Eiichiro Matsubara and Yoshiharu Uchimoto and Zempachi Ogumi",
year = "2014",
month = "10",
day = "7",
doi = "10.1039/c4ta01130a",
language = "English",
volume = "2",
pages = "15414--15419",
journal = "Journal of Materials Chemistry A",
issn = "2050-7488",
publisher = "Royal Society of Chemistry",
number = "37",

}

TY - JOUR

T1 - Kinetically asymmetric charge and discharge behavior of LiNi 0.5Mn1.5O4 at low temperature observed by in situ X-ray diffraction

AU - Takahashi, Ikuma

AU - Murayama, Haruno

AU - Sato, Kenji

AU - Naka, Takahiro

AU - Kitada, Koji

AU - Fukuda, Katsutoshi

AU - Koyama, Yukinori

AU - Arai, Hajime

AU - Matsubara, Eiichiro

AU - Uchimoto, Yoshiharu

AU - Ogumi, Zempachi

PY - 2014/10/7

Y1 - 2014/10/7

N2 - Capacity decrease at low temperatures is one of the issues to be solved for secondary batteries especially for automobile applications and it is thus important to clarify the reaction kinetics in operating batteries and identify the rate determining step that governs the performance at low temperatures. Phase transitions in electrode active materials are important factors that affect the reaction kinetics particularly for thin electrodes used in high power applications. In this study, the phase transition dynamics of thin LiNi 0.5Mn1.5O4 electrodes at various temperatures is examined using electrochemical methods combined with temperature-controlled in situ X-ray diffraction analysis to directly capture the reacting species and elucidate the reaction mechanism. The analysis shows that there occur consecutive phase transitions of LiNi0.5Mn1.5O4 (Li1 phase) ↔ Li0.5Ni0.5Mn1.5O 4 (Li0.5 phase) and the Li0.5 phase ↔ Ni0.5Mn 1.5O4 (Li0 phase) at room temperature and above. At lower temperatures the transition of Li1 → Li0.5 proceeds during the charging process but further delithiation to form the Li0 phase is restricted, leading to the capacity decrease. On the other hand, on discharging at low temperatures the amount of the Li0 phase to be lithiated is limited and this causes the capacity decrease. There is no Li0.5 phase formation on discharging at low temperatures, revealing remarkable kinetic asymmetry of the reaction processes for charging and discharging. It is suggested that the Li0.5 phase formed on discharging is instantly lithiated to form the Li1 phase, due to the small potential gap between the two transitions. These results indicate that the phase transition kinetics of Li0.5 ↔ Li0 is slower than that of Li1 ↔ Li0.5 and the former transition is the rate determining step at low temperatures.

AB - Capacity decrease at low temperatures is one of the issues to be solved for secondary batteries especially for automobile applications and it is thus important to clarify the reaction kinetics in operating batteries and identify the rate determining step that governs the performance at low temperatures. Phase transitions in electrode active materials are important factors that affect the reaction kinetics particularly for thin electrodes used in high power applications. In this study, the phase transition dynamics of thin LiNi 0.5Mn1.5O4 electrodes at various temperatures is examined using electrochemical methods combined with temperature-controlled in situ X-ray diffraction analysis to directly capture the reacting species and elucidate the reaction mechanism. The analysis shows that there occur consecutive phase transitions of LiNi0.5Mn1.5O4 (Li1 phase) ↔ Li0.5Ni0.5Mn1.5O 4 (Li0.5 phase) and the Li0.5 phase ↔ Ni0.5Mn 1.5O4 (Li0 phase) at room temperature and above. At lower temperatures the transition of Li1 → Li0.5 proceeds during the charging process but further delithiation to form the Li0 phase is restricted, leading to the capacity decrease. On the other hand, on discharging at low temperatures the amount of the Li0 phase to be lithiated is limited and this causes the capacity decrease. There is no Li0.5 phase formation on discharging at low temperatures, revealing remarkable kinetic asymmetry of the reaction processes for charging and discharging. It is suggested that the Li0.5 phase formed on discharging is instantly lithiated to form the Li1 phase, due to the small potential gap between the two transitions. These results indicate that the phase transition kinetics of Li0.5 ↔ Li0 is slower than that of Li1 ↔ Li0.5 and the former transition is the rate determining step at low temperatures.

UR - http://www.scopus.com/inward/record.url?scp=84907083549&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84907083549&partnerID=8YFLogxK

U2 - 10.1039/c4ta01130a

DO - 10.1039/c4ta01130a

M3 - Article

AN - SCOPUS:84907083549

VL - 2

SP - 15414

EP - 15419

JO - Journal of Materials Chemistry A

JF - Journal of Materials Chemistry A

SN - 2050-7488

IS - 37

ER -