Yafei Dai

Rational Design of Cathode Structure for High Rate Performance Lithium-Sulfur Batteries.

Practical applications of Li-S batteries require not only high specific capacities and long cycle lifetimes but also high rate performance. We report a rationally designed Li-S cathode, which consists of a freestanding composite thin film assembled from S nanoparticles, reduced graphene oxide (rGO), and a multifunctional additive poly(anthraquinonyl sulfide) (PAQS). The S nanoparticles provide a high initial specific capacity, and the layered and porous rGO structure provides electron and ion transport paths and restricts polysulfide shuttling. PAQS is not only a highly efficient sulfide trapping agent but also an excellent Li(+) conductor, which benefits the battery reaction kinetics at a high rate. The resulting cathode exhibits an initial specific capacity of 1255 mAh g(-1) with a decay rate as low as 0.046% per cycles over 1200 cycles. Importantly, it displays a reversible capacity of 615 mAh g(-1) when discharged at a high rate of 8 C (13.744 A g(-1)).

Mono-Mercury Doping of Au25 and the HOMO/LUMO Energies Evaluation Employing Differential Pulse Voltammetry

Controlling the bimetal nanoparticle with atomic monodispersity is still challenging. Herein, a monodisperse bimetal nanoparticle is synthesized in 25% yield (on gold atom basis) by an unusual replacement method. The formula of the nanoparticle is determined to be Au24Hg1(PET)18 (PET: phenylethanethiolate) by high-resolution ESI-MS spectrometry in conjunction with multiple analyses including X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA). X-ray single-crystal diffraction reveals that the structure of Au24Hg1(PET)18 remains the structural framework of Au25(PET)18 with one of the outer-shell gold atoms replaced by one Hg atom, which is further supported by theoretical calculations and experimental results as well. Importantly, differential pulse voltammetry (DPV) is first employed to estimate the highest occupied molecular orbit (HOMO) and the lowest unoccupied molecular orbit (LUMO) energies of Au24Hg1(PET)18 based on previous calculations.

Energetics, structure, and charge distribution of reduced and oxidized n-pyrrole oligomers: A density functional approach

Polypyrrole is a conjugated polymer prototype of conducting polymers. The energetically preferred spatial conformation of n-pyrrole oligomers (n=1-24) in both the reduced and oxidized phases is obtained and analyzed in this paper within the hybrid density functional theory. Binding energies, gap energies, radius of gyration, end-to-end distance, and vibrational frequencies are reported as functions of oligomer length. Reduced n-pyrrole are bent chains for all sizes showing a dramatic departure from planarity. Vibrational spectra of n-pyrrole oligomers indicate the presence of two fairly size-insensitive frequency regions, which increase in intensity with increasing oligomer size. Several oxidation levels were analyzed for n-pyrrole through the distribution of the carbon-carbon bond orders and single/double bond lengths. It is shown that the oxidation level is directly related to the way positive charge localizes along the n-pyrrole oligomer chain. If charge/n<13, the oligomers are bent and charge is delocalized; if charge/n>/=13, the oligomers are planar and charge notoriously localizes in n/charge regions along the backbone. Calculations with electronegative dopants show that charge localizes in the neighborhood of the dopant. It is demonstrated that one localized state in the gap between the highest occupied and lowest-unoccupied states appears for every +2e in the oxidation level. The band structure of infinite reduced polypyrrole gives a band gap energy in excellent agreement with experiment. The evolution of the band gap and the charge-localized band as a function of polypyrrole oxidation level is reported.

Diffusion and desorption of oxygen atoms on graphene

To understand the reversible oxidation of graphene in a recent experiment, a density-functional theory study is performed. The adsorption energy of isolated oxygen atom on graphene is 2.3xa0eV, indicating a strong interaction between them. However, the migration barrier of oxygen atoms on graphene is only 0.8xa0eV and oxygen diffusion is still possible. Provided with this possibility, we find that, although a single oxygen atom is very difficult to desorb, cooperative desorption of two oxygen atoms is feasible.

Energetics and Vibrational Analysis of Methyl Salicylate Isomers

Energetics and vibrational analysis study of six isomers of methyl salicylate in their singlet ground state and first excited triple state is put forward in this work at the density functional theory level and large basis sets. The ketoB isomer is the lowest energy isomer, followed by its rotamer ketoA. For both ketoB and ketoA their enolized tautomers are found to be stable as well as their open forms that lack the internal hydrogen bond. The calculated vibrational spectra are in excellent agreement with IR experiments of methyl salicylate in the vapor phase. It is demonstrated that solvent effects have a weak influence on the stability of these isomers. The ionization reaction from ketoB to ketoA shows a high barrier of 0.67 eV ensuring that thermal and chemical equilibria yield systems containing mostly the ketoB isomer at normal conditions.

A Density Functional Study of the Nonlinear Optical Properties of Edge-Functionalized Nonplanar Nanographenes

The atomically precise edge chlorination of nanographenes has recently been reported as a crucial technology of functionalization through which the planar structure and optical properties of nanographenes can be significantly changed. To check the effects of molecular size, geometrical symmetry and edge functionalization of nanographenes on their optical properties, a series of nanographenes is studied in the framework of density functional theory with the B3LYP functional. Our results indicate that edge functionalization remarkably changes the nonlinear optical properties and increases the anisotropy of nanographenes compared to the effects of the molecular size and system geometric symmetry. Furthermore, the nonlinear optical properties of nanographenes can be tuned by precise edge functionalization, which opens a new avenue for using nanographenes as nonlinear optical materials.

Monte Carlo study of oligopyrroles in condensed phases

A classical model potential to simulate pyrrole oligomers in condensed phases is developed in this work. The new potential contains ten parameters that are optimized on a database of energy points calculated within the density functional theory approach. Based on this potential the condensed phase of systems composed of pyrrole oligomers with 4 and 12 monomers is studied as a function of system density. The binding energy, end-to-end distance, radius of gyration, vector and orientational order parameters, and pair correlation functions are reported at T=300 K. The mechanical equilibrium density is determined for both systems. The bulk modulus is reported at these densities, showing that systems composed of short oligomers are softer than systems containing longer oligomers. Analysis of pair correlation functions and order parameters indicates that at equilibrium the system of short oligomers has characteristics of a liquid while the system of longer oligomers shows a chain stacking trend.

Cationic Covalent Organic Framework Nanosheets for Fast Li-Ion Conduction

Covalent organic frameworks (COFs) with their porous structures that are accommodative of Li salts are considered to be potential candidates for solid-state fast Li+ conductors. However, Li salts simply infiltrated in the pores of solid-state COFs tend to be present in closely associate ion pairs, resulting in slow ionic diffusion dynamics. Here we incorporate cationic skeleton into the COF structure to split the Li salt ion pair through stronger dielectric screening. It is observed that the concentration of free Li+ ions in the resulting material is drastically increased, leading to a significantly improved Li+ conductivity in the absence of any solvent (up to 2.09 × 10-4 S cm-1 at 70 °C).

Density functional theory study of neutral and oxidized thiophene oligomers

The effect of oxidation on the energetics and structure of thiophene (Th) oligomers is studied with density functional theory at the B3PW91∕6-311++G(d,p) level. Neutral n-Th oligomers (2 < n < 13) are gently curved planar chains. Ionization potential and electron affinity results show that n-Th oligomers are easier to be oxidized as their chain length increases. Oxidation states +2, +4, +6, and +8 are energetically stable in 12-Th. Upon oxidation the conjugated backbone of 12-Th switches from extended benzenoid phase to quinoid phase localized on groups of monomers regularly spaced along the chain. Oxidized states +2, +4, +6, and +8 of 12-Th display two +1e localized at the ends of their chains only because of the finite size of the chains. In 12-Th this end-effect extends over the two terminal monomers forming a positive-negative charge duet. This peculiar charge localization makes n-Th oligomers different from other conducting polymers with similar structure, such as polypyrrole. The spectrum of single-electron molecular states of oxidized 12-Th displays two localized single-electron states in the HOMO-LUMO energy gap per +2 oxidation state. Oligothiophene 12-Th doped with F atoms at 1:2 concentration presents a charge transfer of 3.4 e from oligomer to dopants that increases to 4.8 e in the presence of solvent. The charge distribution in these F-doped oligomers is similar to the +4 oxidation state of 12-Th. It is predicted that dopants produce an enhanced charge transfer localized in the proximity of their locations enhancing the formation of bipolarons in the central part of the oligomer chain.

Energetics, structure, and electron detachment spectra of calcium and zinc neutral and anion clusters: a density functional theory study.

A hybrid density functional approach with very large basis sets was used for studying Ca2 through Ca19 and Zn3 through Zn11 neutral clusters and their cluster anions. Energetics, structure, and vibrational analysis of all these neutral clusters and cluster anions are reported. The calculated electron affinities are in excellent agreement with experiment displaying a characteristic kink at Ca10 and Zn10. This kink occurs because the 10-atom neutral cluster is very stable whereas the cluster anion is not. Additionally, the electron detachment binding energies (BEs) up to Ca6(-) and Zn6(-) were identified by analyzing the ground and excited states of the cluster anions and of their corresponding size neutral clusters. The theoretical BE is in very good agreement with experiment for both calcium and zinc cluster anions. The three main peaks in the spectrum correspond to BEs from the ground state of the cluster anion (doublet) to the ground state of the neutral cluster (singlet) and to the first triplet and quintet excited states of the neutral cluster. The calculated energy gap from the lowest BE peak to the second peak is in excellent agreement with experiment. The calculation reproduces very well the energy gap observed in Ca4(-) and Zn4(-), which is larger than those for other sizes and is indicative of the strong stability of the anion and neutral tetramers.