Mn(II) deposition on anodes and its effects on capacity fade in spinel lithium manganate–carbon systems
- 30 September 2013
- journal article
- research article
- Published by Springer Science and Business Media LLC in Nature Communications
- Vol. 4 (1), 2437
- https://doi.org/10.1038/ncomms3437
Abstract
Dissolution and migration of manganese from cathode lead to severe capacity fading of lithium manganate–carbon cells. Overcoming this major problem requires a better understanding of the mechanisms of manganese dissolution, migration and deposition. Here we apply a variety of advanced analytical methods to study lithium manganate cathodes that are cycled with different anodes. We show that the oxidation state of manganese deposited on the anodes is +2, which differs from the results reported earlier. Our results also indicate that a metathesis reaction between Mn(II) and some species on the solid–electrolyte interphase takes place during the deposition of Mn(II) on the anodes, rather than a reduction reaction that leads to the formation of metallic Mn, as speculated in earlier studies. The concentration of Mn deposited on the anode gradually increases with cycles; this trend is well correlated with the anodes rising impedance and capacity fading of the cell.Keywords
This publication has 41 references indexed in Scilit:
- Correlation between dissolution behavior and electrochemical cycling performance for LiNi1/3Co1/3Mn1/3O2-based cellsJournal of Power Sources, 2012
- Determination of Mn valence states in mixed-valent manganates by XANES spectroscopyAmerican Mineralogist: Journal of Earth and Planetary Materials, 2012
- Elevated temperature cycling stability and electrochemical impedance of LiMn2O4 cathodes with nanoporous ZrO2 and TiO2 coatingsJournal of Power Sources, 2010
- Evidence of Transition-Metal Accumulation on Aged Graphite Anodes by SIMSElectrochemical and Solid-State Letters, 2008
- Enhancement of Li-ion battery performance of graphite anode by sodium ion as an electrolyte additiveElectrochemistry Communications, 2003
- Inorganic electrolyte additives to suppress the degradation of graphite anodes by dissolved Mn(II) for lithium-ion batteriesJournal of Power Sources, 2003
- Influence of manganese(II), cobalt(II), and nickel(II) additives in electrolyte on performance of graphite anode for lithium-ion batteriesElectrochimica Acta, 2002
- The elevated temperature performance of the LiMn2O4/C system: failure and solutionsElectrochimica Acta, 1999
- Dissolution of Spinel Oxides and Capacity Losses in 4 V Li / Li x Mn2 O 4 CellsJournal of the Electrochemical Society, 1996
- Lithium insertion into manganese spinelsMaterials Research Bulletin, 1983