Electrocatalytic Mechanism and Sabatier Principle in C2N-Supported Atomically Dispersed Catalysts for the Sulfur Reduction Reaction in Lithium-Sulfur Batteries.

The sluggish kinetics of the sulfur reduction reaction (SRR) impedes the practical application of lithium-sulfur batteries (LSBs). Electrocatalysts are necessary to expedite the conversion of polysulfides. Here, we systematically investigate the chemical mechanisms and size dependence of catalytic activities toward the SRR from Li2S4 to Li2S on single-, double-, and triple-atom catalysts supported on C2N (Mn@C2N, where M is a 3d transitional metal and n = 1-3) as model systems by using first-principles calculations and a comprehensive electrocatalytic model. Our results reveal that the adsorption strength of the LiS• intermediate is identified as an optimal descriptor for catalytic activity. M1@C2N exhibits superior stability and exceptional activity compared to those of the other two catalyst types. Cu1@C2N exhibits the lowest overpotential of 0.426 V. Li embedding or a prelithiation strategy verifies the therein Sabatier principle. This work emphasizes the precise control of the active site structure and microenvironment in catalytic SRR and offers guidance for the design of electrocatalysts for metal-sulfur batteries.

Revisiting the Role of Physical Confinement and Chemical Regulation of 3D Hosts for Dendrite-Free Li Metal Anode.

Lithium metal anode has been demonstrated as the most promising anode for lithium batteries because of its high theoretical capacity, but infinite volume change and dendritic growth during Li electrodeposition have prevented its practical applications. Both physical morphology confinement and chemical adsorption/diffusion regulation are two crucial approaches to designing lithiophilic materials to alleviate dendrite of Li metal anode. However, their roles in suppressing dendrite growth for long-life Li anode are not fully understood yet. Herein, three different Ni-based nanosheet arrays (NiO-NS, Ni3N-NS, and Ni5P4-NS) on carbon cloth as proof-of-concept lithiophilic frameworks are proposed for Li metal anodes. The two-dimensional nanoarray is more promising to facilitate uniform Li+ flow and electric field. Compared with the NiO-NS and the Ni5P4-NS, the Ni3N-NS on carbon cloth after reacting with molten Li (Li-Ni/Li3N-NS@CC) can afford the strongest adsorption to Li+ and the most rapid Li+ diffusion path. Therefore, the Li-Ni/Li3N-NS@CC electrode realizes the lowest overpotential and the most excellent electrochemical performance (60 mA cm-2 and 60 mAh cm-2 for 1000 h). Furthermore, a remarkable full battery (LiFePO4||Li-Ni/Li3N-NS@CC) reaches 300 cycles at 2C. This research provides valuable insight into designing dendrite-free alkali metal batteries.

Role of the Metal Atom in a Carbon-Based Single-Atom Electrocatalyst for LiS Redox Reactions.

Carbon-based single metal atom catalysts (SACs) are being extensively investigated to improve the kinetics of the Li-S redox reaction, which is greatly important for batteries with cell-level energy densities >500 W h kg-1 . However, there are contradictory reports regarding the electrocatalytic activities of the different metal atoms and the role of the metal atom in LiS chemistry still remains unclear. This is due to the complex relationship between the catalytic behavior and the structure of carbon-based SACs. Here, the catalytic behavior and active-site geometry, oxidation state, and the electronic structure of different metal centers (Fe/Co/Ni) embedded in nitrogen-doped graphene, and having similar physicochemical characteristics, are studied. Combining X-ray absorption spectroscopy, density functional theory calculations, and electrochemical analysis, it is revealed that the coordination-geometry and oxidation state of the metal atoms are modified when interacting with sulfur species. This interaction is strongly dependent on the hybridization of metal 3d and S p-orbitals. A moderate hybridization with the Fermi level crossing the metal 3d band is more favorable for LiS redox reactions. This study thus provides a fundamental understanding of how metal atoms in SACs impact LiS redox behavior and offers new guidelines to develop highly active catalytic materials for high-performance LiS batteries.

Cobalt in Nitrogen-Doped Graphene as Single-Atom Catalyst for High-Sulfur Content Lithium-Sulfur Batteries.

Because of their high theoretical energy density and low cost, lithium-sulfur (Li-S) batteries are promising next-generation energy storage devices. The electrochemical performance of Li-S batteries largely depends on the efficient reversible conversion of Li polysulfides to Li2S in discharge and to elemental S during charging. Here, we report on our discovery that monodisperse cobalt atoms embedded in nitrogen-doped graphene (Co-N/G) can trigger the surface-mediated reaction of Li polysulfides. Using a combination of operando X-ray absorption spectroscopy and first-principles calculation, we reveal that the Co-N-C coordination center serves as a bifunctional electrocatalyst to facilitate both the formation and the decomposition of Li2S in discharge and charge processes, respectively. The S@Co-N/G composite, with a high S mass ratio of 90 wt %, can deliver a gravimetric capacity of 1210 mAh g-1, and it exhibits an areal capacity of 5.1 mAh cm-2 with capacity fading rate of 0.029% per cycle over 100 cycles at 0.2 C at S loading of 6.0 mg cm-2 on the electrode disk.