Sankha Mukherjee

Phosphorene as a Polysulfide Immobilizer and Catalyst in High‐Performance Lithium–Sulfur Batteries

Theoretical and experimental studies together show phosphorene as a highly potent polysulfide immobilizer for lithium-sulfur batteries, enabling a high capacity, good rate capability, and excellent cycling stability.

Nonlinear fracture toughness measurement and crack propagation resistance of functionalized graphene multilayers

Functionalized graphene multilayer is tougher than graphene. Despite promising applications of two-dimensional (2D) materials, one major concern is their propensity to fail in a brittle manner, which results in a low fracture toughness causing reliability issues in practical applications. We show that this limitation can be overcome by using functionalized graphene multilayers with fracture toughness (J integral) as high as ~39 J/m2, measured via a microelectromechanical systems–based in situ transmission electron microscopy technique coupled with nonlinear finite element fracture analysis. The measured fracture toughness of functionalized graphene multilayers is more than two times higher than graphene (~16 J/m2). A linear fracture analysis, similar to that previously applied to other 2D materials, was also conducted and found to be inaccurate due to the nonlinear nature of the stress-strain response of functionalized graphene multilayers. A crack arresting mechanism of functionalized graphene multilayers was experimentally observed and identified as the main contributing factor for the higher fracture toughness as compared to graphene. Molecular dynamics simulations revealed that the interactions among functionalized atoms in constituent layers and distinct fracture pathways in individual layers, due to a random distribution of functionalized carbon atoms in multilayers, restrict the growth of a preexisting crack. The results inspire potential strategies for overcoming the relatively low fracture toughness of 2D materials through chemical functionalization.

Adsorption and Diffusion of Lithium and Sodium on Defective Rhenium Disulfide: A First Principles Study

Single-layer rhenium disulfide (ReS2) is a unique material with distinctive, anisotropic electronic, mechanical, and optical properties and has the potential to be used as an anode in alkali-metal-ion batteries. In this work, first principles calculations were performed to systematically evaluate the potential of monolayer pristine and defective ReS2 as anodes in lithium (Li)- and sodium (Na)-ion batteries. Our calculations suggest that there are several potential adsorption sites for Li and Na on pristine ReS2, owing to its low-symmetry structure. Additionally, the adsorption of Li and Na over pristine ReS2 is very strong with adsorption energies of -2.28 and -1.71 eV, respectively. Interestingly, the presence of point defects causes significantly stronger binding of the alkali-metal atoms with adsorption energies in the range -2.98 to -3.17 eV for Li and -2.66 to -2.92 eV for Na. Re single vacancy was found to be the strongest binding defect for Li adsorption, whereas S single vacancy was found to be the strongest for Na. The diffusion of these two alkali atoms over pristine ReS2 is anisotropic, with an energy barrier of 0.33 eV for Li and 0.16 eV for Na. The energy barriers associated with escaping a double vacancy and single vacancy for Li atoms are significantly large at 0.60 eV for the double-vacancy case and 0.51 eV for the single-vacancy case. Similarly, for Na, they are 0.59 and 0.47 eV, respectively, which indicates slower migration and sluggish charging/discharging. However, the diffusion energy barrier over a Re single vacancy is found to be merely 0.42 eV for a Li atom and 0.28 eV for Na. Overall, S single and double vacancies can reduce the diffusion rate by 103-105 times for Li and Na ions, respectively. These results suggest that monolayer ReS2 with a Re single vacancy adsorbs Li and Na stronger than pristine ReS2, with negligible negotiation with the charging/discharging rate of the battery, and therefore they can be used as an anode in Li- and Na-ion batteries.

Ultrahigh Storage and Fast Diffusion of Na and K in Blue Phosphorene Anodes

In the wake of blue phosphorenes (BP) computational discovery and experimental realization, it has emerged as a versatile material with interesting optical, electrical, and mechanical properties. In this study, using first principles density functional theory calculations, we have investigated the adsorption and diffusion of Na and K over monolayer BP to assess its suitability as Na-ion and K-ion battery anodes. The optimized adsorption energies were found to be -0.96 eV for Na and -1.54 eV for K, which are sufficiently large to ensure stability and safety during operation. In addition, BP could adsorb Na and K atoms up to a stoichiometric ratio of 1:1 which yields a high storage capacity of 865 mA h/g for both adatom species. Through examination of the electronic structure and projected density of states of BP as a function of Na/K concentration, we predict that the band gap of the system increasingly shrinks, and in the case of maximum K adsorption, the band gap diminishes completely. Additionally, the diffusion of Na and K over BP is observed to be ultrafast, especially for K, and anisotropic with modest energy barriers of 0.11 and 0.093 eV for Na and K, respectively. Building upon these findings, we employed vibrational analysis techniques with transition state theory to incorporate kinetic effects and predicted a diffusivity of 7.2 × 10-5 cm2/s for Na and 8.58 × 10-5 cm2/s for K on BP. Given these advantages, that is, ultrahigh capacity, electrical conductivity, and high Na/K diffusivity, we conclude that BP can be considered as an excellent candidate for anodes in Na- and K-ion batteries.

Hydrogen storage in Li, Na and Ca decorated and defective borophene: a first principles study

Recently synthesized two-dimensional (2D) borophene possesses unique structural, mechanical, electrical and optical properties. Herein, we present a comprehensive study of H2 storage in alkali metal decorated and defect containing 2D borophene using density functional theory calculations. While the adsorption of H2 over pristine borophene was found to be weak with a binding energy of −0.045 eV per H2, metal decoration and point defects enhanced the adsorption strength significantly. Interestingly, the magnitudes of binding energy for a single H2 molecule over Li, Na and Ca decorated borophene were found to increase up to −0.36, −0.34, and −0.12 eV per H2, respectively. On the other hand, while the binding energy of one H2 molecule over the borophene substrate containing a single vacancy (SV) was only −0.063 eV per H2, similar to that of phosphorene, the binding energy increased to an enormous −0.69 eV per H2 over borophene containing a double vacancy (DV). To gain further insight into the H2 adsorption process and identify sources of charge transfer, differential charge densities and projected density of states were calculated. Significant charge accumulation and depletion caused strong polarization of the H2 molecules. Finally, Na, Li and Ca decorated borophene yielded the gravimetric densities 9.0%, 6.8%, and 7.6%, respectively. The gravimetric density of the borophene containing a DV was found to be the highest, a staggering 9.2%, owing to increased interactions between DV borophene and the H2 molecules. These results suggest that borophene can be an effective substrate for H2 storage by carefully engineering it with metal decoration and point defects.