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Nat Commun. 2013;4:2437. doi: 10.1038/ncomms3437.

Mn(II) deposition on anodes and its effects on capacity fade in spinel lithium manganate-carbon systems.

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1] Key Laboratory of Organic Optoelectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing 100084, China [2] Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL 60439, USA [3].


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.


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