No abstract

While α-V2O5 has traditionally been considered as a promising oxide to reversibly intercalate high levels of Mg2+ at high potential, recent reports indicate that previously observed electrochemical activity is dominated by intercalation of H+ rather than Mg2+, even in moderately dry nonaqueous electrolytes. Consequently, the inherent functionality of oxides to intercalate Mg2+ remains in question. By conducting electrochemistry in a chemically and anodically stable ionic liquid electrolyte, we report that, at 110 °C, layered α-V2O5 is indeed capable of reversibly intercalating 1 mol Mg2+ per unit formula, to accumulate capacities above 280 mAh g–1. Multimodal characterization confirmed intercalation of Mg2+ by probing the elemental, redox, and morphological changes undergone by the oxide. After cycling at 110 °C, the electrochemical activity at room temperature was significantly enhanced. The results renew prospects for functional Mg rechargeable batteries surpassing the levels of energy density of current Li-ion batteries.

The energy density of rechargeable batteries utilizing metals as anodes surpasses that of Li ion batteries, which employ carbon instead. Among possible metals, magnesium represents a potential alternative to the conventional choice, lithium, in terms of storage density, safety, stability, and cost. However, a major obstacle for metal-based batteries is the identification of electrolytes that show reversible deposition/dissolution of the metal anode and support reversible intercalation of ions into a cathode. Traditional Grignard-based Mg electrolytes are excellent with respect to the reversible deposition of Mg, but their limited anodic stability and compatibility with oxide cathodes hinder their applicability in Mg batteries with higher voltage. Non-Grignard electrolytes, which consist of ethereal solutions of magnesium(II) bis(trifluoromethanesulfonyl)imide (Mg(TFSI)), remain fairly stable near the potential of Mg deposition. The slight reactivity of these electrolytes toward Mg metal can be remedied by the addition of surface-protecting agents, such as MgCl. Hence, ethereal solutions of Mg(TFSI) salt with MgCl as an additive have been suggested as a representative non-Grignard Mg electrolyte. In this work, the degradation mechanisms of a Mg metal anode in the TFSI-based electrolyte were studied using a current density of 1 mA cm and an areal capacity of ∼0.4 mAh cm, which is close to those used in practical applications. The degradation mechanisms identified include the corrosion of Mg metal, which causes the loss of electronic pathways and mechanical integrity, the nonuniform deposition of Mg, and the decomposition of TFSI anions. This study not only represents an assessment of the behavior of Mg metal anodes at practical current density and areal capacity but also details the outcomes of interfacial passivation, which was detected by simple cyclic voltammetry experiments. This study also points out the absolute absence of any passivation at the electrode-electrolyte interface for the premise of developing electrolytes compatible with a metal anode.

LiNi0.5Mn1.5O4 epitomizes the challenges imposed by high electrochemical potential reactivity on the durability of high energy density Li-ion batteries. Postsynthesis coatings have been explored as a solution to these challenges, but the fundamentals of their function have not been ascertained. To contribute to this understanding, the surface of LiNi0.5Mn1.5O4 microparticles was modified with Mg2+, a coating component of literature relevance, using two different heat treatment temperatures, 500 and 800 °C. A combination of characterization tools revealed that Mg2+ was introduced mainly as an inhomogeneous MgO coating in the sample treated at 500 °C, and into the spinel lattice at the subsurface of the particles at 800 °C. Comparing the properties of these two different materials with an unmodified baseline afforded the opportunity to evaluate the effect of varying surface chemistries. Coulometry in Li metal half cells was used as a macroscopic measure of side reactions at the electrode–electrolyte interfaces. This magnitude was comparable in all the materials at room temperature. In contrast, a significant drop in efficiency was observed in the untreated material when the cycling temperature was raised to 50 °C, but not in the modified materials. The origin of the reduced reactivity of the materials after introducing Mg-based modifications was evaluated by probing the chemical changes at the Ni–O bonds using soft XAS. Taken together, the results of this study revealed that incorporation of Mg stabilizes highly oxidized Ni–O species, which can be related to the better stability toward the electrolyte. They point to a pathway toward the guided design of efficient surface modifications to yield battery electrode materials with increased stability against the electrolyte.