Revealing the formation and electrochemical properties of bis(trifluoromethanesulfonyl) imide intercalated graphite with first-principles calculations

Graphite has been reported to have anion as well as cation intercalation capacities as both cathode and anode host materials for the dual ion battery. In this work, we study the intercalation of bis(trifluoromethanesulfonyl) imide (TFSI) anion from ionic liquid electrolyte into graphite with first-principles calculations. We build models for TFSI-C$_n$ compounds with systematically increasing unit cell sizes of graphene sheet and investigate their stabilities by calculating the formation energy, resulting in the linear decrease and arriving at the limit of stability. With identified unit cell sizes for stable compound formation, we reveal that the interlayer distance and relative volume expansion ratio of TFSI-C$_n$ increase as increasing the concentration of TFSI intercalate during the charge process. The electrode voltage is determined to be ranged from 3.8 V to 3.0 V at the specific capacity ranging from 30 mAh g$^{-1}$ to 54 mAh g$^{-1}$ in agreement with experiment. Moreover, a very low activation barrier of under 50 meV for TFSI migration and good electronic conductivity give a proof of using these compounds as a promising cathode. Through the analysis of charge transfer, we clarify the mechanism of TFSI-C$_n$ formation, and reveal new prospects for developing graphite based cathode

Ab initio investigation of the adsorption of zoledronic acid molecule on hydroxyapatite (001) surface: an atomistic insight of bone protection

We report a computational study of the adsorption of zoledronic acid molecule on hydroxyapatite (001) surface within ab initio density functional theory. The systematic study has been performed, from hydroxyapatite bulk and surface, and zoledronic acid molecule to the adsorption of the molecule on the surface. The optimized bond lengths and bond angles were obtained and analyzed, giving an evidence of structural similarity between subjects under study. The formation energies of hydroxyapatite (001) surfaces with two kinds of terminations were computed as about 1.2 and 1.5 J/m^2 with detailed atomistic structural information. We determined the adsorption energies of zoledronic acid molecule on the surfaces, which are -260 kJ/mol at 0.25 ML and -400 kJ/mol at 0.5 ML. An atomistic insight of strong binding affinity of zoledronic acid to the hydroxyapatite surface was given and discussed.Comment: 11 pages, 8 figure

Ab initio study of sodium cointercalation with diglyme molecule into graphite

The cointercalation of sodium with the solvent organic molecule into graphite can resolve difficulty of forming the stage-I Na-graphite intercalation compound, which is a predominant anode of Na-ion battery. To clarify the mechanism of such cointercalation, we investigate the atomistic structure, energetics, electrochemical properties, ion and electron conductance, and charge transferring upon de/intercalation of the solvated Na-diglyme ion into graphite with {\it ab initio} calculations. It is found that the Na(digl)$_2$C$_n$ compound has the negatively lowest intercalation energy at $n\approx$21, the solvated Na(digl)$_2$ ion diffuses fast in the interlayer space, and their electronic conductance can be enhanced compared to graphite. The calculations reveal that the diglyme molecules as well as Na atom donates electrons to the graphene layer, resulting in the formation of ionic bonding between the graphene layer and the moiety of diglyme molecule. This work will contribute to the development of innovative anode materials for alkali-ion battery applications

Influence of halide composition on the structural, electronic, and optical properties of mixed CH3_3NH3_3Pb(I1−x_{1-x}Brx_x)3_3 perovskites calculated using the virtual crystal approximation method

We investigate the structural, electronic and optical properties of mixed bromide-iodide lead perovskite solar cell CH$_3$NH$_3$Pb(I$_{1-x}$Br$_x$)$_3$ by means of the virtual crystal approximation (VCA) within density functional theory (DFT). Optimizing the atomic positions and lattice parameters increasing the bromide content $x$ from 0.0 to 1.0, we fit the calculated lattice parameter and energy band gap to the linear and quadratic function of Br content, respectively, which are in good agreement with the experiment, respecting the Vegard's law. With the calculated exciton binding energy and light absorption coefficient, we make sure that VCA gives consistent results with the experiment, and the mixed halide perovskites are suitable for generating the charge carriers by light absorption and conducting the carriers easily due to their strong photon absorption coefficient, low exciton bindign energy, and high carrier mobility at low Br contents. Furthermore analyzing the bonding lengths between Pb and X (I$_{1-x}$Br$_x$: virtual atom) as well as C and N, we stress that the stability of perovskite solar cell is definitely improved at $x$=0.2

Two-dimensional hybrid composites of SnS2 with graphene and graphene oxide for improving sodium storage: A first-principles study

Among the recent achievements of sodium-ion battery (SIB) electrode materials, hybridization of two-dimentional (2D) materials is one of the most interesting appointments. In this work, we propose to use the 2D hybrid composites of SnS2 with graphene or graphene oxide (GO) layers as SIB anode, based on the first-principles calculations of their atomic structures, sodium intercalation energetics and electronic properties. The calculations reveal that graphene or GO film can effectively support not only the stable formation of hetero-interface with the SnS2 layer but also the easy intercalation of sodium atom with low migration energy and acceptable low volume change. The electronic charge density differences and the local density of state indicate that the electrons are transferred from the graphene or GO layer to the SnS2 layer, facilitating the formation of hetero-interface and improving the electronic conductance of the semiconducting SnS2 layer. These 2D hybrid composites of SnS2/G or GO are concluded to be more promising candidates for SIB anodes compared with the individual monolayers

First-principles study of ternary graphite compounds cointercalated with alkali atoms (Li, Na, and K) and alkylamines towards alkali ion battery applications

Using density functional theory calculations, we have investigated the structural, energetic, and electronic properties of ternary graphite intercalation compounds (GICs) containing alkali atoms (AM) and normal alkylamine molecules (nC$x$), denoted as AM-nC$x$-GICs (AM=Li, Na, K, $x$=1, 2, 3, 4). The orthorhombic unit cells have been used to build the models for crystalline stage-I AM-nC$x$-GICs. By performing the variable cell relaxations and the analysis of results, we have found that with the increase in the atomic number of alkali atoms the layer separations decreases in contrast to AM-GICs, while the bond lengths of alkali atoms with graphene layer and nitrogen atom of alkylamine decreases. The formation and interlayer binding energies of AM-nC3-GICs have been calculated, indicating the increase in stability from Li to K. The calculated energy barriers for migration of alkali atoms suggest that alkali cation with larger ionic radius diffuses in graphite more smoothly, being similar to AM-GICs. The analysis of density of states, electronic density differences, and atomic populations illustrates a mechanism how the insertion of especially Na among alkali atoms into graphite with first stage can be made easy by cointercalation with alkylamine, more extent of electronic charge transfer is occurred from more electropositive alkali atom to carbon ring of graphene layer, while alkylamine molecules interact strongly with graphene layer through the hybridization of valence electron orbitals.Comment: 22 pages, 9 figure

Defect energetics and electronic structures of As-doped p-type ZnO crystals: A first-principles study

First-principles calculations based on density functional theory have been carried out to understand the mechanism of fabricating As-doped p-type ZnO semiconductors. It has been confirmed that AsZn-2VZn complex is the most plausible acceptor among several candidates for p-type doping by computing the formation and ionization energies. The electronic band structures and atomic-projected density of states of AsZn-2VZn defect complex-contained ZnO bulks have been computed. The acceptor level in AsZn-2VZn band structure has found to be 0.12 eV, which is in good agreement with the experimental ionization energy (0.12 ~ 0.18 eV). The hybridization among O 2p, Zn 3d and As 4s states has been observed around the valence band maximum

Role of Water Molecule in Enhancing the Proton Conductivity on Graphene Oxide at Humidity Condition

Recent experimental reports on in-plane proton conduction in reduced graphene oxide (rGO) films open a new way for the design of proton exchange membrane essential in fuel cells and chemical filters. At high humidity condition, water molecules attached on the rGO sheet are expected to play a critical role, but theoretical works for such phenomena have been scarcely found in the literature. In this study, we investigate the proton migration on water-adsorbed monolayer and bilayer rGO sheets using first-principles calculations in order to reveal the mechanism. We devise a series of models for the water-adsorbed rGO films as systematically varying the reduction degree and water content, and optimize their atomic structures in reasonable agreement with the experiment, using a density functional that accounts for van der Waals correction. Upon suggesting two different transport mechanisms, epoxy-mediated and water-mediated hoppings, we determine the kinetic activation barriers for these in-plane proton transports on the rGO sheets. Our calculations indicate that the water-mediated transport is more likely to occur due to its much lower activation energy than the epoxy-mediated one and reveal new prospects for developing efficient solid proton conductors

First-principles study on the chemical decomposition of inorganic perovskites \ce{CsPbI3} and \ce{RbPbI3} at finite temperature and pressure

Inorganic halide perovskite \ce{Cs(Rb)PbI3} has attracted significant research interest in the application of light-absorbing material of perovskite solar cells (PSCs). Although there have been extensive studies on structural and electronic properties of inorganic halide perovskites, the investigation on their thermodynamic stability is lack. Thus, we investigate the effect of substituting Rb for Cs in \ce{CsPbI3} on the chemical decomposition and thermodynamic stability using first-principles thermodynamics. By calculating the formation energies of solid solutions \ce{Cs$_{1-x}$Rb$_x$PbI3} from their ingredients \ce{Cs$_{1-x}$Rb$_x$I} and \ce{PbI2}, we find that the best match between efficiency and stability can be achieved at the Rb content $x\approx$ 0.7. The calculated Helmholtz free energy of solid solutions indicates that \ce{Cs$_{1-x}$Rb$_x$PbI3} has a good thermodynamic stability at room temperature due to a good miscibility of \ce{CsPbI3} and \ce{RbPbI3}. Through lattice-dynamics calculations, we further highlight that \ce{RbPbI3} never stabilize in cubic phase at any temperature and pressure due to the chemical decomposition into its ingredients \ce{RbI} and \ce{PbI2}, while \ce{CsPbI3} can be stabilized in the cubic phase at the temperature range of 0$-$600 K and the pressure range of 0$-$4 GPa. Our work reasonably explains the experimental observations, and paves the way for understanding material stability of the inorganic halide perovskites and designing efficient inorganic halide PSCs

Formation and characterization of ceramic coating from alumino silicate mineral powders in the matrix of cement composite on the concrete wall

Enhancement of thermal performance of concrete wall is nowadays of great importance in reducing the operational energy demand of buildings. We developed a new kind of inorganic coating material based on \ce{SiO2}-\ce{Al2O3}-rich minerals and Portland cement (PC) powder. The finely pulverized mineral powder with the particle size distribution (PSD) of 0.4-40 $\mu$m was mixed with the vehicle solvent containing some agents, cement powder with PSD of 2-100 $\mu$m, and water in the certain weight ratio, producing the colloid solution. After application within 2 hours to the plaster layer of concrete wall and sufficient long hardening period of over three months, the coating layer of 0.6-1.0 mm thickness was observed to become a densified ceramic. Powder X-ray diffraction (XRD) experiments were performed to identify the crystalline components of minerals, cement and ceramic coating powders. Three- and two-dimensional surface morphologies and chemical compositions of coating material were obtained with the optical interferometer and scanning electron microscope (SEM) equipped with an energy dispersive X-ray analyzer (EDX). These XRD and SEM/EDX analyses demonstrated obviously that the coating layer is mainly composed of the calcium-silicate-hydrate (C-S-H) and the calcium-aluminate-hydrate (C-A-H) ceramics with the relatively small number of closed pores (10\% porosity) compared with the cement mortar and concrete layers. Two-step hydrations of cement and subsequently \ce{SiO2}-\ce{Al2O3} promoted by the alkali product \ce{Ca(OH)2} were proposed as the main mechanism of ceramic formation