Understanding Catalytic Mechanisms and Cathode Interface Kinetics in Nonaqueous Mg-CO2 Batteries.

We leverage first-principles density functional theory (DFT) calculations to understand the electrocatalytic processes in Mg-CO2 batteries, considering ruthenium oxide (RuO2) as an archetypical cathode catalyst. Our goal is to establish a mechanistic framework for understanding the charging and discharging reaction pathways and their influence on overpotentials. On the RuO2 (211) surface, we found reaction initiation through thermodynamically favorable adsorption of Mg followed by interactions with CO2. However, we found that the formation of carbonate (CO32-) and oxalate (C2O42-) intermediates via the activation of CO2 at the catalytic site is thermodynamically unfavorable. We predict that MgC2O4 will form as the discharge product due to its lower overpotential compared to MgCO3. However, MgC2O4 is thermodynamically unstable and is expected to decompose into MgCO3, MgO, and C as final discharge products. Through Bader charge analysis, we investigate the covalent interactions between intermediates and catalyst sites. Moreover, we study the electrochemical free energy profiles of the most favorable reaction pathways and determine discharge and charge overpotentials of 1.30 and 1.35 V, respectively. Our results underscore the importance of catalyst design for the cathode material to overcome performance limitations in nonaqueous Mg-CO2 batteries.

Regulating Surface Charge by Embedding Ru Nanoparticles over 2D Hydroxides toward Water Oxidation.

Exploring highly active and earth-abundant electrocatalysts for the oxygen evolution reaction (OER) is considered one of the prime prerequisites for generating green hydrogen. Herein, a competent microwave-assisted decoration of Ru nanoparticles (NPs) over the bimetallic layered double hydroxide (LDH) material is proposed. The same has been used as an OER catalyst in a 1 M KOH solution. The catalyst shows an interesting Ru NP loading dependency toward the OER, and a concentration-dependent volcanic relationship between electronic charge and thermoneutral current densities has been observed. This volcanic relation shows that with an optimum concentration of Ru NPs, the catalyst could effectively catalyze the OER by obeying the Sabatier principle of ion adsorption. The optimized Ru@CoFe-LDH(3%) demands an overpotential value of only 249 mV to drive a current density value of 10 mA/cm2 with the highest TOF value of 14.4 s-1 as compared to similar CoFe-LDH-based materials. In situ impedance experiments and DFT studies demonstrated that incorporating the Ru NPs boosts the intrinsic OER activity of the CoFe-LDH on account of sufficient activated redox reactivities for both Co and lattice oxygen of the CoFe-LDH. As a result, compared with the pristine CoFe-LDH, the current density of Ru@CoFe-LDH(3%) at 1.55 V vs RHE normalized by ECSA increased by 86.58%. First-principles DFT analysis shows that the optimized Ru@CoFe-LDH(3%) possesses a lower d-band center that indicates weaker and more optimal binding characteristics for OER intermediates, improving the overall OER performance. Overall, this report displays an excellent correlation between the decorated concentration of NPs over the LDH surface which can tune the OER activity as verified by both experimental and theoretical calculations.

Lewis Acid Site Assisted Bifunctional Activity of Tin Doped Gallium Oxide and Its Application in Rechargeable Zn-Air Batteries.

The enhanced safety, superior energy, and power density of rechargeable metal-air batteries make them ideal energy storage systems for application in energy grids and electric vehicles. However, the absence of a cost-effective and stable bifunctional catalyst that can replace expensive platinum (Pt)-based catalyst to promote oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) at the air cathode hinders their broader adaptation. Here, it is demonstrated that Tin (Sn) doped ß-gallium oxide (ß-Ga2 O3 ) in the bulk form can efficiently catalyze ORR and OER and, hence, be applied as the cathode in Zn-air batteries. The Sn-doped ß-Ga2 O3 sample with 15% Sn (Snx =0.15 -Ga2 O3 ) displayed exceptional catalytic activity for a bulk, non-noble metal-based catalyst. When used as a cathode, the excellent electrocatalytic bifunctional activity of Snx =0.15 -Ga2 O3 leads to a prototype Zn-air battery with a high-power density of 138 mW cm-2 and improved cycling stability compared to devices with benchmark Pt-based cathode. The combined experimental and theoretical exploration revealed that the Lewis acid sites in ß-Ga2 O3 aid in regulating the electron density distribution on the Sn-doped sites, optimize the adsorption energies of reaction intermediates, and facilitate the formation of critical reaction intermediate (O*), leading to enhanced electrocatalytic activity.

Unveiling the Electrocatalytic Activity of 1T'-MoSe2 on Lithium-Polysulfide Conversion Reactions.

The dissolution of intermediate lithium polysulfides (LiPS) into an electrolyte and their shuttling between the electrodes have been the primary bottlenecks for the commercialization of high-energy density lithium-sulfur (Li-S) batteries. While several two-dimensional (2D) materials have been deployed in recent years to mitigate these issues, their activity is strictly restricted to their edge-plane-based active sites. Herein, for the first time, we have explored a phase transformation phenomenon in a 2D material to enhance the number of active sites and electrocatalytic activity toward LiPS redox reactions. Detailed theoretical calculations demonstrate that phase transformation from the 2H to 1T' phase in a MoSe2 material activates the basal planes that allow for LiPS adsorption. The corresponding transformation mechanism and LiPS adsorption capabilities of the as-formed 1T'-MoSe2 were elucidated experimentally using microscopic and spectroscopic techniques. Further, the electrochemical evaluation of phase-transformed MoSe2 revealed its strong electrocatalytic activity toward LiPS reduction and their oxidation reactions. The 1T'-MoSe2-based cathode hosts for sulfur later provide a superior cycling performance of over 250 cycles with a capacity loss of only 0.15% per cycle along with an excellent Coulombic efficiency of 99.6%.

Elucidating Synergistic Mechanisms of Adsorption and Electrocatalysis of Polysulfides on Double-Transition Metal MXenes for Na-S Batteries.

Multiple unfavorable features, such as poor electronic conductivity of sulfur cathodes, the dissolution and shuttling of sodium polysulfides (Na2Sn) in electrolytes, and the slower kinetics for the decomposition of solid Na2S, make sodium-sulfur batteries (NaSBs) impractical. To overcome these obstacles, novel double-transition metal (DTM) MXenes, Mo2TiC2T2, (T = O and S) are studied as an anchoring material (AM) to immobilize higher-order polysulfides and to expedite the otherwise slower kinetics of insoluble short-chain polysulfides. Density functional theory (DFT) calculations are carried out to justify and compare the effectiveness of Mo2TiC2S2 and Mo2TiC2O2 as AMs by analyzing their interactions with S8/Na2Sn (n = 1, 2, 4, 6, and 8). Mo2TiC2S2 provides moderate adsorption strength compared to Mo2TiC2O2, therefore, it is expected to effectively inhibit Na2Sn dissolution and shuttling without causing decomposition of Na2Sn. The calculated Gibbs free energies of the rate-determining step for sulfur reduction reactions (SRR) are found to be significantly lower (0.791 eV for S and 0.628 eV for O functionalization) than that in vacuum (1.442 eV), suggesting that the SRR is more thermodynamically favorable on Mo2TiC2T2 during discharge. Additionally, both Mo2TiC2S2 and Mo2TiC2O2 demonstrated effective electrocatalytic activity for the decomposition of Na2S, with a substantial reduction in the energy barrier to 1.59 eV for Mo2TiC2S2 and 1.67 eV for Mo2TiC2O2. While Mo2TiC2O2 had superior binding properties, structural distortion is observed in Na2Sn, which may adversely affect cyclability. On the other hand, because of its moderate binding energy, enhanced electronic conductivity, and significantly faster oxidative decomposition kinetics of polysulfides, Mo2TiC2S2 can be considered as an effective AM for suppressing the shuttle effect and improving the performance of NaSBs.

Mechanistic Insights into Interactions of Polysulfides at VS2 Interfaces in Na-S Batteries: A DFT Study.

Room temperature sodium-sulfur (Na-S) batteries, because of their high theoretical energy density and low cost, are considered as a promising candidate for next-generation energy storage devices. However, the practical utilization of the Na-S batteries is greatly hindered by various deleterious factors such as dissolution of sodium polysulfides (Na2Sn) into the electrolyte commonly termed as "shuttle effect," sluggish decomposition of solid Na2S, and poor electronic conductivity of sulfur. To overcome the challenges, we introduced single-layer vanadium disulfide (VS2) as an anchoring material (AM) to immobilize higher-order polysulfides from the dissolution and also to accelerate the otherwise sluggish kinetics of insoluble short-chain polysulfides. We employ density functional theory (DFT) calculations to elucidate the Na2Sn interactions at the VS2 interfaces. We show that the adsorption strengths of various Na2Sn species on the VS2 basal plane are adequate (1.21-4.3 eV) to suppress the shuttle effect, and the structure of Na2Sn are maintained without any decomposition, which is necessary to mitigate capacity fading. The calculated projected density of states (PDOS) reveals that the metallic character of the pristine VS2 is retained even after Na2Sn adsorption. The calculated Gibbs free energy of each elementary sulfur reduction reaction indicates a significant decrement in the free energy barrier due to the catalytic activity of the VS2 surface. Furthermore, VS2 is found to be an excellent catalyst to significantly reduce the oxidative decomposition barrier of Na2S, which facilitates accelerated electrode kinetics and higher utilization of sulfur. Overall, VS2 with strong adsorption behavior, enhanced electronic conductivity, and improved oxidative decomposition kinetics of polysulfides can be considered as an effective AM to prevent the shuttle effect and to improve the performance of Na-S batteries.

Phonon thermal conductivity of the stanene/hBN van der Waals heterostructure.

We use classical non-equilibrium molecular dynamics (NEMD) simulations to investigate the phonon thermal conductivity (PTC) of hexagonal boron nitride (hBN) supported stanene. At first, we examine the length dependent PTCs of bare stanene and hBN, and the stanene/hBN heterostructure and realize the dominance of the hBN layer to dictate the PTC in the heterostructure system. Afterward, we assess the length-independent bulk PTCs of these materials. The bulk PTCs at room temperature are found as ∼15.20 W m-1 K-1, ∼550 W m-1 K-1, and ∼232 W m-1 K-1 for bare stanene and hBN, and stanene/hBN, respectively. Moreover, our simulations reveal that bare stanene exhibits a substantially lower PTC compared to bare hBN, and the predicted PTC of stanene/hBN lies between those of stand-alone stanene and hBN. We also found that the PTC obtained for the stanene/hBN system from NEMD simulations nicely agrees with the theoretical formula developed to predict the PTC of heterostructures of two distinct materials. Temperature studies suggest that the PTC of the stanene/hBN heterostructure system follows a decreasing trend with increasing temperature. Additionally, corresponding phonon density of states (PDOS) and phonon dispersion data are provided to comprehensively understand the phonon properties of bare stanene and hBN, and stanene/hBN. Overall, this NEMD study would offer a deep understating towards the PTC of the stanene/hBN heterostructure and would widen the scope of its successful operations in future nanoelectronic, spintronic, and thermoelectric devices.

Atomic-scale analysis of the physical strength and phonon transport mechanisms of monolayer ß-bismuthene.

Bismuthene has opened up a new avenue in the field of nanotechnology because of its spectacular electronic and thermoelectric features. The strong spin-orbit-coupling enables its operation as the largest nontrivial bandgap topological insulator and quantum spin hall material at room temperature, which is unlikely for any other 2D material. It is also known to be the most promising thermoelectric material due to its remarkable thermoelectric properties, including a substantially high power factor. However, an in-depth understanding of the mechanical and thermal transport properties of bismuthene is crucial for its practical implementation and efficient operation. Employing the Stillinger-Weber potential, we utilized molecular dynamics simulations to inspect the mechanical strength and thermal conductivity of the monolayer ß-bismuthene for the first time. We analyzed the effect of temperature on the tensile mechanical properties along the armchair and zigzag directions of bismuthene nanosheets and found that increasing temperature causes a significant deterioration in these properties. The material shows superior fracture resistance with zigzag loading, whereas the armchair direction exhibits an improved elasticity. Next, we showed that increasing vacancy concentration and crack length notably reduce the fracture stress and strain of ß-bismuthene. Under all these conditions, ß-bismuthene showed a strong chirality effect under tensile loading. We also explored the fracture phenomena of a pre-cracked ß-bismuthene, which reveal that the armchair-directed crack possesses a higher fracture resistance than the zigzag-directed crack. Interestingly, branching phenomena occurred during crack propagation for the armchair crack; meanwhile, the crack propagates perpendicular to loading for the zigzag crack. Afterward, we investigated the effect of loading rate on the fracture properties of bismuthene along the armchair and zigzag directions. Finally, we calculated the thermal conductivity of bismuthene under the influence of temperature and vacancy and recorded a substantial decrement in thermal conductivity with increasing temperature and vacancy. The obtained results are comprehensively discussed in the light of phonon density of states, phonon dispersion spectrum, and phonon group velocities. It is also disclosed that the thermal conductivity of ß-bismuthene is considerably lower than that of other analogous honeycomb structures. This study can add a new dimension to the successful realization of bismuthene in future (opto)electronic, spintronic, and thermoelectric devices.

Functionalized MXenes as effective polyselenide immobilizers for lithium-selenium batteries: a density functional theory (DFT) study.

The practical applications of lithium selenium (Li-Se) batteries are impeded primarily due to the dissolution and migration of higher-order polyselenides (Li2Sen) into the electrolyte (known as the shuttle effect) and inactive deposition of lower-order polyselenides. The high electrical conductivity and mechanical strength of MXenes make them a suitable candidate to provide adequate anchoring to prevent polyselenide dissolution and improved electrochemical performance. Herein, we used density functional theory (DFT) calculations to understand the binding mechanism of Li2Sen on graphene and surface-functionalized Ti3C2 MXenes. We used graphene as a reference material to assess Li2Sen binding strengths on functionalized Ti3C2X2 (where X = S, O, F, and Cl). We observed that Ti3C2S2 and Ti3C2O2 exhibit superior anchoring behavior compared to graphene, Ti3C2F2, and Ti3C2Cl2. The calculated Li2Sen adsorption strengths, provided by S- and O-terminated Ti3C2, are greater than those of the commonly used ether-based electrolyte, which is a requisite for effective suppression of Li2Sen shuttling. Ti3C2X2 and graphene with adsorbed Li2Sen retain their structural integrity without chemical decomposition. Density of states (DOS) analysis demonstrates that the conductive behavior of Ti3C2X2 is preserved even after Li2Sen adsorption, which can provide electronic pathways to stimulate the redox electrochemistry of Li2Sen. Overall, our unprecedented simulation results reveal superior anchoring behavior of Ti3C2S2 and Ti3C2O2 for Li2Sen adsorption, and this developed understanding can be leveraged for designing carbon-free Ti3C2 MXene-based selenium cathode materials to boost the electrochemical performance of Li-Se batteries.