Issue 3, 2016

Phase transition kinetics of LiNi0.5Mn1.5O4 analyzed by temperature-controlled operando X-ray absorption spectroscopy

Abstract

LiNi0.5Mn1.5O4 (LNMO) is a promising positive electrode material for lithium ion batteries because it shows a high potential of 4.7 V vs. Li/Li+. Its charge–discharge reaction includes two consecutive phase transitions between LiNi0.5Mn1.5O4 (Li1) ↔ Li0.5Ni0.5Mn1.5O4 (Li0.5) and Li0.5 ↔ Ni0.5Mn1.5O4 (Li0) and the complex transition kinetics that governs the rate capability of LNMO can hardly be analyzed by simple electrochemical techniques. Herein, we apply temperature-controlled operando X-ray absorption spectroscopy to directly capture the reacting phases from −20 °C to 40 °C under potential step (chronoamperometric) conditions and evaluate the phase transition kinetics using the apparent first-order rate constants at various temperatures. The constant for the Li1 ↔ Li0.5 transition (process 1) is larger than that for the Li0.5 ↔ Li0 transition (process 2) at all the measured temperatures, and the corresponding activation energies are 29 and 46 kJ mol−1 for processes 1 and 2, respectively. The results obtained are discussed to elucidate the limiting factor in this system as well as in other electrode systems.

Graphical abstract: Phase transition kinetics of LiNi0.5Mn1.5O4 analyzed by temperature-controlled operando X-ray absorption spectroscopy

Supplementary files

Article information

Article type
Paper
Submitted
16 Sep 2015
Accepted
03 Dec 2015
First published
21 Dec 2015

Phys. Chem. Chem. Phys., 2016,18, 1897-1904

Author version available

Phase transition kinetics of LiNi0.5Mn1.5O4 analyzed by temperature-controlled operando X-ray absorption spectroscopy

I. Takahashi, H. Arai, H. Murayama, K. Sato, H. Komatsu, H. Tanida, Y. Koyama, Y. Uchimoto and Z. Ogumi, Phys. Chem. Chem. Phys., 2016, 18, 1897 DOI: 10.1039/C5CP05535K

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements