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].
Nat Commun. 2013;4:2437. doi: 10.1038/ncomms3437.
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.
从阴极到正极的锰溶解和迁移会导致锰酸锂-碳电池的容量严重衰减。要克服这个主要问题,需要更好地了解锰溶解、迁移和沉积的机制。在这里,我们应用各种先进的分析方法来研究与不同阳极循环的锰酸锂正极。我们表明,沉积在阳极上的锰的氧化态为+2,这与早期报道的结果不同。我们的结果还表明,在 Mn(II)沉积在阳极上的过程中,Mn(II)与固体电解质界面上的某些物质之间发生了复分解反应,而不是导致形成金属 Mn 的还原反应,这与早期研究的推测不同。沉积在阳极上的 Mn 的浓度随着循环逐渐增加;这一趋势与阳极阻抗的增加和电池容量的衰减密切相关。