An operando dual-edge X-ray absorption spectroscopy on both transition-metal ordered and disordered LiNi0.5Mn1.5O4 during electrochemical delithiation and lithiation was carried out. The large data set was analyzed via a chemometric approach to gain reliable insights into the redox activity and the local structural changes of Ni and Mn throughout the electrochemical charge and discharge reaction. Our findings confirm that redox activity relies predominantly on the Ni2+/4+ redox couple involving a transient Ni3+ phase. Interestingly, a reversible minority contribution of Mn3+/4+ is also evinced in both LNMO materials. While the reaction steps and involved reactants of both ordered and disordered LNMO materials generally coincide, we highlight differences in terms of reaction dynamics as well as in local structural evolution induced by the TM ordering.

Silicon-based anodes are extensively studied as an alternative to graphite for lithium ion batteries. However, silicon particles suffer larges changes in their volume (about 280%) during cycling, which lead to particles cracking and breakage of the solid electrolyte interphase. This process induces continuous irreversible electrolyte decomposition that strongly reduces the battery life. In this research work, different silicon@graphite anodes have been prepared through a facile and scalable ball milling synthesis and have been tested in lithium batteries. The morphology and structure of the different samples have been studied using X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, and scanning and transmission electron microscopy. We show how the incorporation of an organic solvent in the synthesis procedure prevents particles agglomeration and leads to a suitable distribution of particles and intimate contact between them. Moreover, the importance of the microstructure of the obtained silicon@graphite electrodes is pointed out. The silicon@graphite anode resulted from the wet ball milling route, which presents capacity values of 850 mA h/g and excellent capacity retention at high current density (≈800 mA h/g at 5 A/g).

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Silicon–graphite (Si@G) anodes are receiving increasing attention because the incorporation of Si enables lithium-ion batteries to reach higher energy density. However, Si suffers from structure rupture due to huge volume changes (ca. 300%). The main challenge for silicon-based anodes is improving their long-term cyclabilities and enabling their charge at fast rates. In this work, we investigate the performance of Si@G composite anode, containing 30 wt.% Si, coupled with a LiNi0.8Co0.15Al0.05O2 (NCA) cathode in a pouch cell configuration. To the best of our knowledge, this is the first report on an NCA/Si@G pouch cell cycled at the 5C rate that delivers specific capacity values of 87 mAh g−1. Several techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and gas chromatography–mass spectrometry (GC–MS) are used to elucidate whether the electrodes and electrolyte suffer irreversible damage when a high C-rate cycling regime is applied, revealing that, in this case, electrode and electrolyte degradation is negligible.