Ammonia treatment of 0.35Li2MnO3·0.65LiNi0.35Mn0.45Co0.20O2 Material: Insights from solid-state NMR analysis

Nicole Leifer, Irina Matlahov, Evan M. Erickson, Hadar Sclar, Florian Schipper, Ji Yong Shin, Christoph Erk, Frederick François Chesneau, Jordan Lampert, Boris Markovsky, Doron Aurbach, Gil Goobes

Research output: Contribution to journalArticlepeer-review

19 Scopus citations

Abstract

Li-rich cathode materials of the formula xLi2MnO3·yLiNiaCobMncO2 (x + y = 1, a + b + c = 1) boast very high discharge capacity, ca. 250 mAh/g. Yet, they suffer capacity decrease and average voltage fade during cycling in Li-ion batteries that prohibit their commercialization. Treatment of the materials with NH3(g) at high temperatures produces improved electrodes with higher stability of capacity and average voltage. The present study follows the changes occurring in the materials upon treatment with ammonia gas, through 6Li and 7Li solid-state NMR investigations of the untreated and ammonia treated 0.35Li2MnO3·0.65LiNi0.35Mn0.45Co0.20O2 as well as its constituent phases, Li2MnO3 and LiNi0.4Co0.2Mn0.4O2. The NMR analysis demonstrates the biphasic nature of these materials. Furthermore, it shows that the Li2MnO3 component phase in the integrated material is the phase mostly being affected by the gas treatment. A thickening of a protective surface film in the integrated material, with the right exposure time to the reactive gas, is observed, which further precludes Ni leach out from the bulk and leads to improved electrode performance. Formation of minor electrochemically inactive oxide phases in the integrated material and similarly in the Li2MnO3 alone upon longer exposure to the gas suggests that the performance deterioration observed can be linked to the rearrangement of ions in the Li2MnO3 constituent phase in the integrated material.

Original languageEnglish
Pages (from-to)3773-3779
Number of pages7
JournalJournal of Physical Chemistry C
Volume122
Issue number7
DOIs
StatePublished - 22 Feb 2018

Bibliographical note

Publisher Copyright:
© 2018 American Chemical Society.

Funding

Partial support for this work was obtained from BASF, Germany, and from the Israel Committee of Higher Education and Ministry of the Prime Minister, Israel, in the framework of the Israel National Research Center for Electrochemical Propulsion (INREP) project.

FundersFunder number
Israel Committee of Higher Education and Ministry of the Prime Minister
Israel National Research Center for Electrochemical Propulsion
BASF

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