Ermias Girma Leggesse

Theoretical study of the reductive decomposition of 1,3-propane sultone: SEI forming additive in lithium-ion batteries

The role of 1,3-propane sultone (PS) as an electrolyte additive for lithium ion batteries is explained by investigating the electroreductive decomposition of PS and (PS)Li+(PC)n (n = 0,1) with the aid of density functional theory calculations. In the gas phase, the PS reductive decomposition is thermodynamically unfavorable as supported by the positive Gibbs free energy change and the negative gas phase vertical electron affinity values for the addition of an electron to give the radical anion intermediate. However, it is possible that PS can undergo one- as well as two-electron reduction processes in bulk solvent. The origin of this difference is explained by examining the frontier molecular orbitals of PS and its reduction intermediate both in solution and gas phase. A solvated PS is reduced prior to PC to give a stable intermediate which then undergo decomposition to yield a more stable primary radical. The products from the termination reactions of the primary radical (Li2SO3, (CH–CH2–CH2–OSO2Li)2, and Li–C carbides) and (PC–Li(O2S)O(CH2)3)2 from the reduction of (PC)–Li+(PS) would build up an effective solid electrolyte interphase.

A First Principles study on Boron-doped Graphene decorated by Ni-Ti-Mg atoms for Enhanced Hydrogen Storage Performance.

We proposed a new solid state material for hydrogen storage, which consists of a combination of both transition and alkaline earth metal atoms decorating a boron-doped graphene surface. Hydrogen adsorption and desorption on this material was investigated using density functional theory calculations. We find that the diffusion barriers for H atom migration and desorption energies are lower than for the previously designed mediums and the proposed medium can reach the gravimetric capacity of ~6.5 wt % hydrogen, which is much higher than the DOE target for the year 2015. Molecular Dynamics simulations show that metal atoms are stably adsorbed on the B doped graphene surface without clustering, which will enhance the hydrogen storage capacity.

Improved Interfacial Properties of MCMB Electrode by 1-(Trimethylsilyl)imidazole as New Electrolyte Additive To Suppress LiPF6 Decomposition

Trace water content in the electrolyte causes the degradation of LiPF6, and the decomposed products further react with water to produce HF, which alters the surface of anode and cathode. As a result, the reaction of HF and the deposition of decomposed products on electrode surface cause significant capacity fading of cells. Avoiding these phenomena is crucial for lithium ion batteries. Considering the Lewis-base feature of the N-Si bond, 1-(trimethylsilyl)imidazole (1-TMSI) is proposed as a novel water scavenging electrolyte additive to suppress LiPF6 decomposition. The scavenging ability of 1-TMSI and beneficiary interfacial chemistry between the MCMB electrode and electrolyte are studied through a combination of experiments and density functional theory (DFT) calculations. NMR analysis indicated that LiPF6 decomposition by water was effectively suppressed in the presence of 0.2 vol % 1-TMSI. XPS surface analysis of MCMB electrode showed that the presence of 1-TMSI reduced deposition of ionic insulating products caused by LiPF6 decomposition. The results showed that the cells with 1-TMSI additive have better performance than the cell without 1-TMSI by facilitating the formation of solid-electrolyte interphase (SEI) layer with better ionic conductivity. It is hoped that the work can contribute to the understanding of SEI and the development of electrolyte additives for prolonged cycle life with improved performance.

Methanol decomposition reactions over a boron-doped graphene supported Ru–Pt catalyst

The decomposition of methanol is currently attracting research attention due to the potential widespread applications of its end products. In this work, density functional theory (DFT) calculations have been performed to investigate the adsorption and decomposition of methanol on a Ru-Pt/boron doped graphene surface. We find that the most favorable reaction pathway is methanol (CH3OH) decomposition through O-H bond breaking to form methoxide (CH3O) as the initial step, followed by further dehydrogenation steps which generate formaldehyde (CH2O), formyl (CHO), and carbon monoxide (CO). The calculations illustrate that CH3OH and CO groups prefer to adsorb at the Ru-top sites, while CH2OH, CH3O, CH2O, CHO, and H2 groups favor the Ru-Pt bridge sites, indicating the preference of Ru atoms to adsorb the active intermediates or species having lone-pair electrons. Based on the results, it is found that the energy barrier for CH3OH decomposition through the initial O-H bond breaking is less than its desorption energy of 0.95 eV, showing that CH3OH prefers to undergo decomposition to CH3O rather than direct desorption. The study provides in-depth theoretical insights into the potentially enhanced catalytic activity of Ru-Pt/boron doped graphene surfaces for methanol decomposition reactions, thereby contributing to the understanding and designing of an efficient catalyst under optimum conditions.