Effect of lithium-trapping on nitrogen-doped graphene as an anchoring material for lithium-sulfur batteries: a density functional theory study.

N-Doped graphene (NG) has been widely used as a cathode material for lithium-sulfur (Li-S) batteries due to its strong interaction with lithium polysulfide (LiPS) species. However, strong interaction between the NG substrate and the LiPS molecules induces undesirable molecular structure decomposition of LiPS. Due to the strong interaction between Li and NG, Li-trapping occurs during battery operation. Therefore, in this study, Li-trapped NG (LiNG) is introduced as a possible structure of NG, and the structural stability of LiNG under applied electric potential is examined. The effect of Li-trapping on the properties of NG as an anchoring material for Li-S batteries is investigated using density functional theory calculations. Li-trapping relieves the strong interaction between NG and LiPS, thereby avoiding decomposition of the LiPS molecule. Although the interaction between the LiPS molecule and the substrate is weakened, additionally formed interaction after Li-trapping, which is between Li in the substrate and S in the molecule, enables LiNG to suppress the shuttle effect. LiNG shows advanced anchoring behavior that suppresses the shuttle effect without any molecular decomposition of LiPS. This finding provides a further understanding of the effect of Li-trapping on the anchoring properties of NG for Li-S batteries.

Theoretical Approach toward Optimum Anion-Doping on MXene Catalysts for Hydrogen Evolution Reaction: an Ab Initio Thermodynamics Study.

Developing highly active catalysts for hydrogen evolution reaction based on earth-abundant materials is challenging. Nitrogen doping has recently been reported to improve catalytic properties by modifying the electrochemical properties of titanium carbide MXene. However, systematic doping engineering, such as optimization of doping concentration, doping site, and thermodynamic phase stabilization have not been systematically controlled, which retards the reliable production of high-activity MXene catalysts. In this study, the optimum doping concentration of nitrogen and doping process conditions on O-functionalized Ti2C MXene for hydrogen evolution reaction were investigated using density functional theory with thermodynamics. To confirm the optimum nitrogen concentration, the catalytic properties are examined considering the Gibbs free energy of hydrogen adsorption and conductivity for 2.2-11.0 at % nitrogen concentration. It was confirmed that 8.8 at % nitrogen-doped Ti2CO2 had optimum catalytic properties under standard conditions. Moreover, when the doping concentration was higher, the decrease in the adsorption energies of hydrogen and the transition in the energy dispersion of the conduction band led to deterioration of the catalytic properties. Through theoretical results, the feasible process conditions for optimum nitrogen concentration while maintaining the structure of MXene are presented using a thermodynamics model taking into account chemical reactions with various nitrogen sources. This study provides further understanding of the nitrogen-doping mechanism of Ti2CO2 for hydrogen evolution reactions.

Poly(fluorenyl aryl piperidinium) membranes and ionomers for anion exchange membrane fuel cells.

Low-cost anion exchange membrane fuel cells have been investigated as a promising alternative to proton exchange membrane fuel cells for the last decade. The major barriers to the viability of anion exchange membrane fuel cells are their unsatisfactory key components-anion exchange ionomers and membranes. Here, we present a series of durable poly(fluorenyl aryl piperidinium) ionomers and membranes where the membranes possess high OH- conductivity of 208 mS cm-1 at 80 °C, low H2 permeability, excellent mechanical properties (84.5 MPa TS), and 2000 h ex-situ durability in 1 M NaOH at 80 °C, while the ionomers have high water vapor permeability and low phenyl adsorption. Based on our rational design of poly(fluorenyl aryl piperidinium) membranes and ionomers, we demonstrate alkaline fuel cell performances of 2.34 W cm-2 in H2-O2 and 1.25 W cm-2 in H2-air (CO2-free) at 80 °C. The present cells can be operated stably under a 0.2 A cm-2 current density for ~200 h.