On the oxidation state of manganese ions in li-ion battery electrolyte solutions

Anjan Banerjee, Yuliya Shilina, Baruch Ziv, Joseph M. Ziegelbauer, Shalom Luski, Doron Aurbach, Ion C. Halalay

Research output: Contribution to journalArticlepeer-review

105 Scopus citations


We demonstrate herein that Mn3+ and not Mn2+, as commonly accepted, is the dominant dissolved manganese cation in LiPF6-based electrolyte solutions of Li-ion batteries with lithium manganate spinel positive and graphite negative electrodes chemistry. The Mn3+ fractions in solution, derived from a combined analysis of electron paramagnetic resonance and inductively coupled plasma spectroscopy data, are ∼80% for either fully discharged (3.0 V hold) or fully charged (4.2 V hold) cells, and ∼60% for galvanostatically cycled cells. These findings agree with the average oxidation state of dissolved Mn ions determined from X-ray absorption near-edge spectroscopy data, as verified through a speciation diagram analysis. We also show that the fractions of Mn3+ in the aprotic nonaqueous electrolyte solution are constant over the duration of our experiments and that disproportionation of Mn3+ occurs at a very slow rate.

Original languageEnglish
Pages (from-to)1738-1741
Number of pages4
JournalJournal of the American Chemical Society
Issue number5
StatePublished - 8 Feb 2017

Bibliographical note

Funding Information:
This work used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357.

Publisher Copyright:
© 2017 American Chemical Society.


Dive into the research topics of 'On the oxidation state of manganese ions in li-ion battery electrolyte solutions'. Together they form a unique fingerprint.

Cite this