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Crystallographic Analysis of Structural Changes in Lithium Nickel Manganese Cobalt Oxides at Different Stages of Lithiation

Tuesday, 21 June 2016
Riverside Center (Hyatt Regency)
K. Fröhlich, J. Kahr (AIT Austrian Institute of Technology GmbH), I. Abrahams (Queen Mary University of London), and A. Trifonova (Austrian Institute of Technology GmbH)
Mixed transition metal oxides are among the most promising cathode materials for lithium ion batteries. The high specific capacity, low cost and thermal stability makes Li(Ni1/3Mn1/3Co1/3)O2, so-called NMC, an excellent material for power tool applications. Therefore, main leading battery manufacturer focus on the combination of these three transition metals to combine the strengths of each of them [1].

The development and design of battery materials require deep understanding of the relations between chemistry, structure and its properties. Nowadays, the commercialized NMC can only reach around 60 % of its theoretical capacity when cycled up to 4.2 V. Higher specific capacities might be reached when the upper voltage limit is raised up to 4.5 V [2], but the lifetime of the cathode then decreases drastically. The deintercalation of more than 0.6 moles of lithium in the charge process of the battery leads to irreversible capacity losses.

Lithium nickel manganese cobalt oxides with different transition metal ratios were successfully synthesized via coprecipitation route. The cathode materials were characterized physico- and electrochemically and the composition was confirmed via inductive coupled plasma atomic emission spectroscopy (ICP-AES).

Structural changes of non-symmetric NMC compounds at different stages of lithiation were recorded using x-ray diffraction. The resulting patterns were analyzed and the structures refined using the Rietveld method implemented in the GSAS (General Structure Analysis System) package [3].

The same procedure of crystallographic characterization of the NMC structure was carried out for different transition metal ratios cycled up to 4.5 V. The results are presented and comparison between symmetric and non-symmetric lithium nickel manganese cobalt oxides will give better insight into structural changes at higher voltages and the relation to their compositions.

Acknowledgement

This work was financially supported by the Austrian Federal Ministry for Transport, Innovation and Technology (bmvit) and the Austrian Research Promotion Agency (FFG).

[1]     N. Yabuuchi, T. Ohzuku, Journal of Power Sources 119-121 (2003): 171-174

[2]     Q. Yu, Z. Chen, L. Xing, D. Chen, H. Rong, Q. Liu,W. Li, Electrochimica Acta 176 (2015): 919-925

[3]     A. C. Larson, R. B. Von Dreele, Los Alamos National Laboratory Report, No. LAUR-86-748, (1987)