Structural insights into the formation and voltage degradation of lithium- and manganese-rich layered oxides.

Hua, Weibo; Wang, Suning; Knapp, Michael; Leake, Steven J; Senyshyn, Anatoliy; Richter, Carsten; Yavuz, Murat; Binder, Joachim R et al. · Nat Commun · 2019

basic_science · Level V

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Abstract

One major challenge in the field of lithium-ion batteries is to understand the degradation mechanism of high-energy lithium- and manganese-rich layered cathode materials. Although they can deliver 30 % excess capacity compared with today's commercially- used cathodes, the so-called voltage decay has been restricting their practical application. In order to unravel the nature of this phenomenon, we have investigated systematically the structural and compositional dependence of manganese-rich lithium insertion compounds on the lithium content provided during synthesis. Structural, electronic and electrochemical characterizations of Li<sub>x</sub>Ni<sub>0.2</sub>Mn<sub>0.6</sub>O<sub>y</sub> with a wide range of lithium contents (0.00 ≤ x ≤ 1.52, 1.07 ≤ y < 2.4) and an analysis of the complexity in the synthesis pathways of monoclinic-layered Li[Li<sub>0.2</sub>Ni<sub>0.2</sub>Mn<sub>0.6</sub>]O<sub>2</sub> oxide provide insight into the underlying processes that cause voltage fading in these cathode materials, i.e. transformation of the lithium-rich layered phase to a lithium-poor spinel phase via an intermediate lithium-containing rock-salt phase with release of lithium/oxygen.