Magnesium Anode Pretreatment Using a Titanium Complex for Magnesium Battery

Although magnesium batteries have received a great deal of attention as a promising power source, the native oxide layer on the Mg surface significantly impedes practical applications, because of the sluggish kinetic behavior of Mg-ion deposition and dissolution. Here, a new approach to improve electrochemical reactivity of Mg anode is proposed, based on chemical pretreatment of the Mg anode using a titanium complex, Ti­(TFSI)₂Cl₂, that effectively removes the native oxide layer on the Mg anode surface. The pretreatment of the Mg anode by Ti­(TFSI)₂Cl₂ remarkably decreases the binding affinity between Mg and O via the formation of a multicoordinate complex (Mg–O–Ti). Thereafter, a series of chemical reactions cleave the Mg–O bonds, resulting in a fresh Mg surface. This creates a cell comprised of the Ti­(TFSI)₂Cl₂-pretreated Mg anode, glyme-based electrolytes, and cathode material that exhibits reversible electrochemical behavior at the electrode/electrolyte interface, resulting in practical applicability and good electrochemical performance

Anion Engineering for Stabilizing Li Interstitial Sites in Halide Solid Electrolytes for All-Solid-State Li Batteries

Halide solid electrolytes (SEs) have been highlighted for their high-voltage stability. Among the halide SEs, the ionic conductivity has been improved by aliovalent metal substitutions or choosing a ccp-like anion-arranged monoclinic structure (C2/m) over hcp- or bcc-like anion-arranged structures. Here, we present a new approach, hard-base substitution, and its underlying mechanism to increase the ionic conductivity of halide SEs. The oxygen substitution to Li2ZrCl6 (trigonal, hcp) increased the ionic conductivity from 0.33 to 1.3 mS cm–1 at Li3.1ZrCl4.9O1.1 (monoclinic, ccp), while the sulfur and fluorine substitutions were not effective. A systematic comparison study revealed that the energetic stabilization of interstitial sites for Li migration plays a key role in improving the ionic conductivity, and the ccp-like anion sublattice is not sufficient to achieve high ionic conductivity. We further examined the feasibility of the oxyhalide SE for practical and all-solid-state battery applications

Bi-Morphological Form of SiO₂ on a Separator for Modulating Li-Ion Solvation and Self-Scavenging of Li Dendrites in Li Metal Batteries

The lithium (Li) metal anode is highly desirable for high-energy density batteries. During prolonged Li plating–stripping, however, dendritic Li formation and growth are probabilistically high, allowing physical contact between the two electrodes, which results in a cell short-circuit. Engineering the separator is a promising and facile way to suppress dendritic growth. When a conventional coating approach is applied, it usually sacrifices the bare separator structure and severely increases the thickness, ultimately decreasing the volumetric density. Herein, we introduce dielectric silicon oxide with the feature of bi-morphological form, i.e., backbone-covered and backbone-anchored, onto the conventional polyethylene separator without any volumetric change. These functionally vary the Li+ transference number and the ionic conductivity so as to modulate Li-ion solvation and self-scavenging of Li dendrites. The proposed separator paves the way to maximizing the full cell performance of Li/NCM622 toward practical application