Interfacial “Single‐Atom‐in‐Defects” Catalysts Accelerating Li⁺ Desolvation Kinetics for Long‐Lifespan Lithium‐Metal Batteries

Abstract

The lithium‐metal anode is a promising candidate for realizing high‐energy‐density batteries owing to its high capacity and low potential. However, several rate‐limiting kinetic obstacles, such as the desolvation of Li+ solvation structure to liberate Li+, Li0 nucleation, and atom diffusion, cause heterogeneous spatial Li‐ion distribution and fractal plating morphology with dendrite formation, leading to low Coulombic efficiency and depressive electrochemical stability. Herein, differing from pore sieving effect or electrolyte engineering, atomic iron anchors to cation vacancy‐rich Co1−xS embedded in 3D porous carbon (SAFe/CVRCS@3DPC) is proposed and demonstrated as catalytic kinetic promoters. Numerous free Li ions are electrocatalytically dissociated from the Li+ solvation complex structure for uniform lateral diffusion by reducing desolvation and diffusion barriers via SAFe/CVRCS@3DPC, realizing smooth dendrite‐free Li morphologies, as comprehensively understood by combined in situ/ex situ characterizations. Encouraged by SAFe/CVRCS@3DPC catalytic promotor, the modified Li‐metal anodes achieve smooth plating with a long lifespan (1600 h) and high Coulombic efficiency without any dendrite formation. Paired with the LiFePO4 cathode, the full cell (10.7 mg cm−2) stabilizes a capacity retention of 90.3% after 300 cycles at 0.5 C, signifying the feasibility of using interfacial catalysts for modulating Li behaviors toward practical applications.

Understanding the Role of Titanium Metal–Organic Framework Nanosheets in Modulating Anode Chemistry for Aqueous Zinc-Ion Batteries

“…To evaluate the effectiveness of Ti MOF NSs, electrochemical measurements were conducted (1 M ZnSO 4 electrolyte). As shown in Figure 3a, compared with bare planar Cu, Ti MOF modification, especially nanosheets, can effectively reduce the zinc plating overpotential by promoting the desolvation and interfacial diffusion dynamics of Zn 2+ , 54 consistent with the results of cyclic voltammetry (CV) (Figure S17). Meanwhile, the Ti MOF NS-protected Cu||Zn cell delivered a higher Coulombic efficiency (CE) (Figure 3b) with much more stabilized cycling.…”

Accelerating High-Rate Li-Ion Storage in Graphite via a Thin-Layer Coating of Atomic Mo–NC

“…Li dendrites formed outside of Gr can penetrate the solid electrolyte interface (SEI), increase the irreversible capacity, and even pierce through the separator, which ultimately induces dangerous short circuits and thermal runaway. 9 Many strategies have been developed to address the above problems, including structural engineering and porosity management for a shortened Li + transport pathway, 10,11 electrolyte regulation for optimal Li + −solvent interaction, 12−14 interface engineering for stable SEI formation, 15 lowered desolvation barriers, 16,17 and fast charge transfer. 18,19 Among them, the interface constructed by graphite/SEI/solvent is of utter importance because it involves several key steps during Li insertion and extraction processes, including Li + desolvation, 20, 21 Li + migration through SEI, 22 charge transfer at Gr edges, 23 Li + diffusion into Gr, 24 etc.…”

“…Many strategies have been developed to address the above problems, including structural engineering and porosity management for a shortened Li + transport pathway, , electrolyte regulation for optimal Li + –solvent interaction, − interface engineering for stable SEI formation, lowered desolvation barriers, , and fast charge transfer. , Among them, the interface constructed by graphite/SEI/solvent is of utter importance because it involves several key steps during Li insertion and extraction processes, including Li + desolvation, , Li + migration through SEI, charge transfer at Gr edges, Li + diffusion into Gr, etc. Therefore, it is essential to devote more attention to this specific area and also vital to construct optimal interface modifications of Gr to achieve fast and stable charging of LIBs.…”

Constructing an Anion-Braking Separator to Regulate Local Li+ Solvation Structure for Stabilizing Lithium Metal Batteries

“…32,33,35−37 As pointed, the Li plating behaviors have close relationships with interfacial electrolyte/electrode information evolution and corresponding Li(solvents) + −anion solvation shell structures. 38 Previous studies point out that dissociating the Li + solvents rapidly could provide many bare Li + flux. 39,40 Meanwhile, regulating the anion-related solvation structure state could indeed improve the dissociation kinetics through constructing suitable pore engineering or active catalysts or electrolyte additives.…”