Remarkably Improved Electrochemical Performance of Li- and Mn-Rich Cathodes upon Substitution of Mn with Ni

Prasant Kumar Nayak, Judith Grinblat, Elena Levi, Tirupathi Rao Penki, Mikhael Levi, Yang Kook Sun, Boris Markovsky, Doron Aurbach

Research output: Contribution to journalReview articlepeer-review

39 Scopus citations

Abstract

Li- and Mn-rich transition-metal oxides of layered structure are promising cathodes for Li-ion batteries because of their high capacity values, ≥250 mAh g-1. These cathodes suffer from capacity fading and discharge voltage decay upon prolonged cycling to potential higher than 4.5 V. Most of these Li- and Mn-rich cathodes contain Ni in a 2+ oxidation state. The fine details of the composition of these materials may be critically important in determining their performance. In the present study, we used Li1.2Ni0.13Mn0.54Co0.13O2 as the reference cathode composition in which Mn ions are substituted by Ni ions so that their average oxidation state in Li1.2Ni0.27Mn0.4Co0.13O2 could change from 2+ to 3+. Upon substitution of Mn with Ni, the specific capacity decreases but, in turn, an impressive stability was gained, about 95% capacity retention after 150 cycles, compared to 77% capacity retention for Li1.2Ni0.13Mn0.54Co0.13O2 cathodes when cycled at a C/5 rate. Also, a higher average discharge voltage of 3.7 V is obtained for Li1.2Ni0.27Mn0.4Co0.13O2 cathodes, which decreases to 3.5 V after 150 cycles, while the voltage fading of cathodes comprising the reference material is more pronounced. The Li1.2Ni0.27Mn0.4Co0.13O2 cathodes also demonstrate higher rate capability compared to the reference Li1.2Ni0.13Mn0.54Co0.13O2 cathodes. These results clearly indicate the importance of the fine composition of cathode materials containing the five elements Li, Mn, Ni, Co, and O. The present study should encourage rigorous optimization efforts related to the fine composition of these cathode materials, before external means such as doping and coating are applied.

Original languageEnglish
Pages (from-to)4309-4319
Number of pages11
JournalACS applied materials & interfaces
Volume9
Issue number5
DOIs
StatePublished - 8 Feb 2017

Bibliographical note

Publisher Copyright:
© 2016 American Chemical Society.

Funding

This work was partially supported by the Israel Science Foundation as part of the INREP project and also by the Israel Ministry of Science and Technology in the framework of the Israel-India binational collaboration program.

FundersFunder number
Israel Science Foundation
Ministry of science and technology, Israel

    Keywords

    • Li- and Mn-rich cathodes
    • Li-ion batteries
    • Mn substitution by Ni
    • impedance
    • voltage stabilization

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