Mixed eldfellite compounds \ce{Na(Fe_{1/2}M_{1/2})(SO4)2} (M = Mn, Co, Ni): A new family of high electrode potential cathodes for the sodium-ion battery

Natural abundance of sodium and its similar behavior to lithium triggered recent extensive studies of cost-effective sodium-ion batteries (SIBs) for large-scale energy storage systems. A challenge is to develop electrode materials with a high electrode potential, specific capacity and a good rate capability. In this work we propose mixed eldfellite compounds \ce{Na_x(Fe_{1/2}M_{1/2})(SO4)2} (M = Mn, Co, Ni) as a new family of high electrode potential cathodes of SIBs and present their material properties predicted by first-principles calculations. The structural optimizations show that these materials have significantly small volume expansion rates below 5\% upon Na insertion/desertion with negative Na binding energies. Through the electronic structure calculations, we find band insulating properties and hole (and/or electron) polaron hoping as a possible mechanism for the charge transfer. Especially we confirm the high electrode voltages over 4 V with reasonably high specific capacities. We also investigate the sodium ion mobility by estimating plausible diffusion pathways and calculating the corresponding activation barriers, demonstrating the reasonably fast migrations of sodium ions during the operation. Our calculation results indicate that these mixed eldfellite compounds can be suitable materials for high performance SIB cathodes

Advances in Modelling and Simulation of Halide Perovskites for Solar Cell Applications

Perovskite solar cells (PSCs) are attracting great attention as the most promising candidate for the next generation solar cells. This is due to their low cost and high power conversion efficiency in spite of their relatively short period of development. Key components of PSCs are a variety of halide perovskites with ABX3 stoichiometry used as a photoabsorber, which brought the factual breakthrough in the field of photovoltaic (PV) technology with their outstanding optoelectronic properties. To commercialize PSCs in the near future, however, these materials need to be further improved for a better performance, represented by high efficiency and high stability. As in other materials development, atomistic modelling and simulation can play a significant role in finding new functional halide perovskites as well as revealing the underlying mechanisms of their material processes and properties. In this sense, computational works for the halide perovskites, mostly focusing on first-principles works, are reviewed with an eye looking for an answer how to improve the performance of PSCs. Specific modelling and simulation techniques to quantify material properties of the halide perovskites are also presented. Finally, the outlook for the challenges and future research directions in this field is provided

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

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

Ionic Diffusion and Electronic Transport in Eldfellite Nax_xFe(SO4_4)2_2

Discovering new electrodes for sodium-ion battery requires clear understanding of the material process during battery operation. Using first-principles calculations, we identify mechanisms of ionic diffusion and electronic transfer in newly developed cathode material, eldfellite Na$_x$Fe(SO$_4$)$_2$, reproducing the electrochemical properties in good agreement with experiment. The inserted sodium atom is suggested to diffuse along the two-dimensional pathway with preceding movement of the host sodium atom, and the activation energy is calculated to be reasonable for fast insertion. We calculate the electronic properties, showing the band insulating at low composition of inserted sodium, for which the electron polaron formation and hoping are also suggested. Our results may contribute to opening a new way of developing innovative cathode materials based on iron and sulfate ion

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

First-principles study on the electronic and optical properties of inorganic perovskite Rb1-xCsxPbI3 for solar cell applications

Recently, replacing or mixing organic molecules in the hybrid halide perovskites with the inorganic Cs or Rb cations has been reported to increase the material stability with the comparable solar cell performance. In this work, we systematically investigate the electronic and optical properties of all-inorganic alkali iodide perovskites Rb1-xCsxPbI3 using the first-principles virtual crystal approximation calculations. Our calculations show that as increasing the Cs content x, lattice constants, band gaps, exciton binding energies, and effective masses of charge carriers decrease following the quadratic (linear for effective masses) functions, while static dielectric constants increase following the quadratic function, indicating an enhancement of solar cell performance upon the Rb addition to CsPbI3. When including the many-body interaction within the GW approximation and incorporating the spin-orbit coupling (SOC), we obtain more reliable band gap compared with experiment for CsPbI3, highlighting the importance of using GW+SOC approach for the all-inorganic as well as organic-inorganic hybrid halide perovskite materials

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