Initial SEI formation in LiBOB-, LiDFOB- and LiBF4-containing PEO electrolytes.

A limiting factor for solid polymer electrolyte (SPE)-based Li-batteries is the functionality of the electrolyte decomposition layer that is spontaneously formed at the Li metal anode. A deeper understanding of this layer will facilitate its improvement. This study investigates three SPEs - polyethylene oxide:lithium tetrafluoroborate (PEO:LiBF4), polyethylene oxide:lithium bis(oxalate)borate (PEO:LiBOB), and polyethylene oxide:lithium difluoro(oxalato)borate (PEO:LiDFOB) - using a combination of electrochemical impedance spectroscopy (EIS), galvanostatic cycling, in situ Li deposition photoelectron spectroscopy (PES), and ab initio molecular dynamics (AIMD) simulations. Through this combination, the cell performance of PEO:LiDFOB can be connected to the initial SPE decomposition at the anode interface. It is found that PEO:LiDFOB had the highest capacity retention, which is correlated to having the least decomposition at the interface. This indicates that the lower SPE decomposition at the interface still creates a more effective decomposition layer, which is capable of preventing further electrolyte decomposition. Moreover, the PES results indicate formation of polyethylene in the SEI in cells based on PEO electrolytes. This is supported by AIMD that shows a polyethylene formation pathway through free-radical polymerization of ethylene.

The use of multicomponent reactions in the development of bis-boronic acids for the detection of ß-sialic acid.

Sialic acid (SA) is a naturally occurring monosaccharide found in glycoproteins and glycolipids. Changes in the expression of SA are associated with several diseases; thus, the detection of SA is of great significance for biological research, cancer diagnosis, and treatment. Boronic acid analogs have emerged as a promising tool for detecting sugars such as SA due to its reversible covalent bonding ability. In this study, 11 bis-boronic acid compounds and 2 mono-boronic acid compounds were synthesized via a highly efficient Ugi-4CR strategy. The synthesized compounds were subjected to affinity fluorescence binding experiments to evaluate their binding capability to SA. Compound A1 was shown to have a promising binding constant of 2602 ± 100 M-1 at pH = 6.0. Density Functional Theory (DFT) calculations examining the binding modes between A1 and SA indicated that the position of the boronic acid functional group was strongly correlated with its interaction with SA's α-hydroxy acid unit. The DFT calculations were consistent with the observations from the fluorescence experiments, demonstrating that the number and relative positions of the boronic acid functional groups are critical factors in enhancing the binding affinity to SA. DFT calculations of both S and R configuration of A1 indicated that the effect of the S/R configuration of A1 on its binding with ß-sialic acid was insignificant as the Ugi-4CR generated racemic products. A fluorine atom was incorporated into the R2 substituent of A1 as an electron-withdrawing group to produce A5, which possessed a significantly higher capability to bind to SA (Keq = 7015 ± 5 M-1 at pH = 6.0). Finally, A1 and A5 were shown to possess exceptional binding selectivity toward ß-sialic acid under pH of 6.0 and 6.5 while preferring to bind with glucose, fructose, and galactose under pH of 7.0 and 7.5.

Lewis Acid Probe for Basicity of Sulfide Electrolytes Investigated by 11B Solid-State NMR.

Sulfide-based solid-state lithium-ion batteries (SSLIB) have attracted a lot of interest globally in the past few years for their high safety and high energy density over the traditional lithium-ion batteries. However, sulfide electrolytes (SEs) are moisture-sensitive which pose significant challenges in the material preparation and cell manufacturing. To the best of our knowledge, there is no tool available to probe the types and the strength of the basic sites in sulfide electrolytes, which is crucial for understanding the moisture stability of sulfide electrolytes. Herein, we propose a new spectral probe with the Lewis base indicator BBr3 to probe the strength of Lewis basic sites on various sulfide electrolytes by 11B solid-state NMR spectroscopy (11B-NMR). The active sulfur sites and the corresponding strength of the sulfide electrolytes are successfully evaluated by the proposed Lewis base probe. The probed strength of the active sulfur sites of a sulfide electrolyte is consistent with the results of DFT (density functional theory) calculation and correlated with the H2S generation rate when the electrolyte was exposed in moisture atmosphere. This work paves a new way to investigate the basicity and moisture stability of the sulfide electrolytes.

Synergistic dual electrolyte additives for fluoride rich solid-electrolyte interface on Li metal anode surface: Mechanistic understanding of electrolyte decomposition.

Improving the quality of the solid-electrolyte interphase (SEI) layer is highly imperative to stabilize the Li-metal anodes for the practical application of high-energy-density batteries. However, controllably managing the formation of robust SEI layers on the anode is challenging in state-of-the-art electrolytes. Herein, we discuss the role of dual additives fluoroethylene carbonate (FEC) and lithium difluorophosphate (LiPO2F2, LiPF) within the commercial electrolyte mixture (LiPF6/EC/DEC) considering their reactivity with Li metal anodes using density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. Synergistic effects of dual additives on SEI formation mechanisms are explored systematically by invoking different electrolyte mixtures including pure electrolyte (LP47), mono-additive (LP47/FEC and LP47/LiPF), and dual additives (LP47/FEC/LiPF). The present work suggests that the addition of dual additives accelerates the reduction of salt and additives while increasing the formation of a LiF-rich SEI layer. In addition, calculated atomic charges are applied to predict the representative F1s X-ray photoelectron (XPS) signal, and our results agree well with the experimentally identified SEI components. The nature of carbon and oxygen-containing groups resulting from the electrolyte decompositions at the anode surface is also analyzed. We find that the presence of dual additives inhibits undesirable solvent degradation in the respective mixtures, which effectively restricts the hazardous side products at the electrolyte-anode interface and improves SEI layer quality.

Exploiting High-Voltage Stability of Dual-Ion Aqueous Electrolyte Reinforced by Incorporation of Fiberglass into Zwitterionic Hydrogel Electrolyte.

Rechargeable zinc aqueous batteries are key alternatives for replacing toxic, flammable, and expensive lithium-ion batteries in grid energy storage systems. However, these systems possess critical weaknesses, including the short electrochemical stability window of water and intrinsic fast zinc dendrite growth. Hydrogel electrolytes provide a possible solution, especially cross-linked zwitterionic polymers that possess strong water retention ability and high ionic conductivity. Herein, an in situ prepared fiberglass-incorporated dual-ion zwitterionic hydrogel electrolyte with an ionic conductivity of 24.32 mS cm-1 , electrochemical stability window up to 2.56 V, and high thermal stability is presented. By incorporating this hydrogel electrolyte of zinc and lithium triflate salts, a zinc//LiMn0.6 Fe0.4 PO4 pouch cell delivers a reversible capacity of 130 mAh g-1 in the range of 1.0-2.2 V at 0.1C, and the test at 2C provides an initial capacity of 82.4 mAh g-1 with 71.8% capacity retention after 1000 cycles with a coulombic efficiency of 97%. Additionally, the pouch cell is fire resistant and remains safe after cutting and piercing.

A method for modelling polymer electrolyte decomposition during the Li-nucleation process in Li-metal batteries.

Elucidating the complex degradation pathways and formed decomposition products of the electrolytes in Li-metal batteries remains challenging. So far, computational studies have been dominated by studying the reactions at inert Li-metal surfaces. In contrast, this study combines DFT and AIMD calculations to explore the Li-nucleation process for studying interfacial reactions during Li-plating by introducing Li-atoms close to the metal surface. These Li-atoms were added into the PEO polymer electrolytes in three stages to simulate the spontaneous reactions. It is found that the highly reactive Li-atoms added during the simulated nucleation contribute to PEO decomposition, and the resulting SEI components in this calculation include lithium alkoxide, ethylene, and lithium ethylene complexes. Meanwhile, the analysis of atomic charge provides a reliable guideline for XPS spectrum fitting in these complicated multicomponent systems. This work gives new insights into the Li-nucleation process, and experimental XPS data supporting this computational strategy. The AIMD/DFT approach combined with surface XPS spectra can thus help efficiently screen potential polymer materials for solid-state battery polymer electrolytes.

The remarkable performance of a single iridium atom supported on hematite for methane activation: a density functional theory study.

Methane is the major component of natural gas, and it significantly contributes to global warming. In this study, we investigated methane activation on the α-Fe2O3(110) surface and M/α-Fe2O3(110) surfaces (M = Ag, Ir, Cu, or Co) using the density-functional theory (DFT) + U method. Our study shows that the Ir/α-Fe2O3(110) surface is a more effective catalyst for C-H bond activation than other catalyst surfaces. We have applied electron density difference (EDD), density of states (DOS), and Bader charge calculations to confirm the cooperative CH⋯O and agostic interactions between CH4 and the Ir/α-Fe2O3(110) surface. To further modify the reactivity of the Ir/α-Fe2O3(110) surface towards methane activation, we conducted a study of the effect of oxygen vacancy (OV) on C-H activation and CH4 dehydrogenation. In the comparison of pristine α-Fe2O3(110), Ir/α-Fe2O3(110), and Ir/α-Fe2O3(110)-OV surfaces, the Ir/α-Fe2O3(110)-OV surface is the best in terms of CH4 adsorption energy and C-H bond elongation, whereas the Ir/α-Fe2O3(110) surface catalyst has the lowest C-H bond activation barrier for the CH4 molecule. The calculations indicate that the Ir/α-Fe2O3(110)-OV surface could be a candidate catalyst for CH4 dehydrogenation reactions.

Combined Density Functional Theory and Microkinetics Study to Predict Optimum Operating Conditions of Si(100) Surface Carbonization by Acetylene for High Power Devices.

The Si(100) surface carbonization mechanisms by acetylene are explored using density functional theory calculations combined with microkinetic simulations. The most stable acetylene adsorption geometries and their subsequent decomposition mechanisms to form a carbon dimer on the Si surface are investigated. Microkinetics simulations are further used to examine the optimal reaction conditions for obtaining a single-crystalline silicon carbide (SiC). We find that the carbon dimer (C2*) as an end-bridge structure can be formed at 560 K, and the maximum of C2* can be obtained near 640 K. The acetylene adsorbed via the di-σ configuration starts to dehydrogenate when the heating rate is too fast and will form two possible carbon dimers (di-C2* and C2*), which will lead to a polycrystalline SiC buffer layer. We predict that 750 K and 10-6 bar will be the optimum temperature and pressure for obtaining a single-crystalline SiC buffer layer, respectively.

The investigation of methane storage at the Ni-MOF-74 material: a periodic DFT calculation.

To develop a high-performance methane storage material, an understanding of the mechanism and electronic interactions between methane and the material is essential. In this study, we performed detailed theoretical analyses to investigate the methane storage capacity of Ni-MOF-74 using a large-scale periodic DFT code CONQUEST. In a single pore of the unit cell, we considered three possible sites, iSBU, L, and P sites, where iSBU is the inorganic secondary building unit with a metal center, and L is the linker consisting of the organic building unit, while the P site is the vacuum site in the center of the pore. It shows that the methane molecule adsorption possesses the largest methane molecule adsorption energy on the iSBU site. Our calculations indicate that both C-HO and weak agostic interactions exist between the methane molecule and the iSBU site. The adsorption energy of one methane molecule on the iSBU site is in good agreement with previous experimental and theoretical studies. The calculation of the stepwise methane molecule adsorption shows that the first six methane molecules can first occupy the iSBU sites via C-HO and weak agostic interactions. The second six methane molecules are adsorbed on the remaining L sites, where the C-Hπ interaction becomes important, leading to the synergistic effect together with the C-HO interaction to enhance the adsorption energy of the methane molecule. Finally, it can adsorb up to sixteen CH4 molecules in a single pore of a unit cell at Ni-MOF-74. Moreover, we conducted DOS and EDD analyses, which clearly show that the interactions play a vital role in the adsorption of a methane molecule on Ni-MOF-74, especially the C-HO interaction.

New Insights into the N-S Bond Formation of a Sulfurized-Polyacrylonitrile Cathode Material for Lithium-Sulfur Batteries.

Sulfurized polyacrylonitrile (S-cPAN) has been recognized as a particularly promising cathode material for lithium-sulfur (Li-S) batteries due to its ultra-stable cycling performance and high degree of sulfur utilization. Though the synthetic conditions and routes for modification of S-cPAN have been extensively studied, details of the molecular structure of S-cPAN remain yet unclear. Herein, a more reasonable molecular structure consisting of pyridinic/pyrrolic nitrogen (NPD/NPL) is proposed, based on the analysis of combined X-ray photoelectron spectroscopy, 13C/15N solid-state nuclear magnetic resonance, and density functional theory data. The coexistence of vicinal NPD/NPL entities plays a vital role in attracting S2 molecules and facilitating N-S bond formation apart from the generally accepted C-S bond in S-cPAN, which could explain the extraordinary electrochemical features of S-cPAN among various nitrogen-containing sulfurized polymers. This study provides new insights and a better understanding of structural details and relevant bond formation mechanisms in S-cPAN, providing a foundation for the design of new types of sulfurized cathode materials suitable for application in next-generation high-performance Li-S batteries.

Theoretical insight into hydroxyl production via H2O2 decomposition over the Fe3O4(311) surface.

Fenton's reagent provides a method to produce active hydroxyl radicals (˙OH) for chemical oxidation by mixing iron oxide and hydrogen peroxide, which divides into homogeneous and heterogeneous Fenton's reagent. Heterogeneous Fenton's reagent is fabricated from H2O2 and various iron oxide solid materials, such as α-FeOOH, α-Fe2O3, and Fe3O4. Fe3O4 possesses the Fe2+/Fe3+ mixed valence oxidational state and has been reported to have good catalytic activity. However, the reaction mechanism of H2O2 decomposition on Fe3O4 surfaces is still unclear. In this work, we performed DFT calculations to investigate the H2O2 decomposition mechanisms over the Fe3O4(311) surface. There are two iron environments for H2O2 adsorption and decomposition on the Fe3O4(311) surface, a Fe2+/Fe3+ environment and a Fe3+/Fe3+ environment. We found that the H2O2 can adsorb on the Fe2+/Fe3+ environment by molecular adsorption but by dissociative adsorption on the Fe3+/Fe3+ environment. Our results show that both adsorption structures can produce two OH groups on the Fe3O4(311) surface thermodynamically. In addition, based on the electronic property analysis, H2O2 on the Fe2+/Fe3+ environment follows the Haber-Weiss mechanism to form one OH anion and one OH radical. On the other hand, H2O2 on the Fe3+/Fe3+ environment follows the radical mechanism to form two OH radicals. In particular, the OH radical formed on Fe2+/Fe3+ has energy levels on both sides of the Fermi energy level. It can be expected that this OH radical has good redox activity.

Theoretical study on the interaction of iodide electrolyte/organic dye with the TiO2 surface in dye-sensitized solar cells.

The iodide/triiodide interaction with the dye on a semiconductor surface plays a significant role in understanding the dye-sensitized solar cells (DSSCs) mechanism and improving its efficiency. In the present study, density functional theory (DFT) calculations were used to determine the interaction between the complexed iodide redox couple with dye/TiO2 for the relevance of DSSCs. Three new metal-free organic dyes noted as D1Y, D2Y and D3Y, featured with D-π-A configuration were designed by varying functional groups on the donor moiety. We analyzed the structural and electronic properties of these dyes when standing alone and being adsorbed on the oxide surface with the iodide electrolyte. Of the designed dyes, the incorporation of a strong donor unit in D1Y and D2Y sensitizers in conjunction with iodide electrolytes on the TiO2 surface provides better adsorption and electronic properties in comparison to those from the dye alone on the TiO2 surface. Analysis of density of states (DOS) indicates that the introduction of a strong electron-donating group into the organic dye, mainly D1Y and D2Y with an iodide electrolyte on the surface remarkably upshifts the Fermi energy, thereby improving the efficiency of the DSSCs by an increase of the open-circuit voltage (Voc). The present finding constitutes the basis for achieving a deeper understanding of the intrinsic interaction taking place at the electrolyte/dye/TiO2 interface and provides us with directions for the design of efficient dyes and redox electrolytes for improving DSSCs.

Enhanced moisture stability of cesium lead iodide perovskite solar cells - a first-principles molecular dynamics study.

An understanding of the interaction of water with perovskite is crucial in improving the structural stability of the perovskite. Hence, in this study, the structural and electronic properties of the γ-CsPbI3(220) perovskite surface upon the adsorption of water molecules have been investigated based on density functional theory calculations. Also, we perform first-principles ab initio molecular dynamics simulations (AIMD) to explore the structural stability of the γ-CsPbI3(220) perovskite surface in the presence of water molecules, and the results are compared with the conventional cubic CH3NH3PbI3(100) perovskite surface. The water molecules show stronger interactions with the (220) surface of γ-CsPbI3 than the (100) surface of CH3NH3PbI3. However, AIMD results demonstrate that the former is much more stable, and no trace of surface degradation was observed upon the adsorption of water molecules.

B, N-co-doped graphene-supported Ir and Pt clusters for methane activation and C─C coupling: A density functional theory study.

Methane conversion by using transition metal catalysts plays in an important role in various usages of the industrial process. The mechanism of methane conversion on B, N-co-doped graphene supported Ir and Pt clusters, BNG-Ir4 and BNG-Pt4, have been investigated using density functional theory calculations. Methane was found to adsorb on BNG-Ir4 and BNG-Pt4 clusters via strong agostic interactions. The first step of methane dehydrogenation on BNG-Ir4 has a lower energy barrier, indicating a facile methane dissociation on BNG-Ir4. In addition, it shows that hydrogen molecule can form on the BNG-Ir4 and hydrogen can desorb from the surface. Besides, the C-C coupling reaction of CH3 to form ethane is a more thermodynamically favorable process than CH3 dehydrogenation on BNG-Ir4. Further, ethane is easier to desorb from the surface due to its low desorption energy. Therefore, the BNG-Ir4 cluster is a potential catalyst for activating methane to form ethane and to produce hydrogen. © 2019 Wiley Periodicals, Inc.

Understanding the Role of Dopant Metal Atoms on the Structural and Electronic Properties of Lithium-Rich Li1.2Ni0.2Mn0.6O2 Cathode Material for Lithium-Ion Batteries.

Improving the stability of lithium-rich cathode materials is important in refining the overall performance of lithium-ion batteries. Here, we have proposed doping of different metal atoms such as K+, Ca2+, Cd2+, and Al3+ in different sites of Li1.2Ni0.2Mn0.6O2, and we have investigated their structural and electronic properties using first-principles calculations. We found that the Ni ions in the pristine Li1.2Ni0.2Mn0.6O2 structure maintained the +3 oxidation state for a longer time and resulted in the structural deformation during the long cycling process. Whereas, the Ni ions in the Cd-, K-, and Ca-doped Li1.2Ni0.2Mn0.6O2 structure are in the +3 oxidation state for a very short time, compared to the pristine system. Our density functional theory (DFT) results show that the doping of the Cd ion in the Ni site of Li1.2Ni0.2Mn0.6O2 is the most suitable one, because it inhibits structural change, decreases the formation energy, and suppresses the Jahn-Teller distortion, compared with the pristine system and other dopant atoms. This theoretical study gives new insight about doping strategy and will help in improving the electrochemical performance of Li-rich cathode materials.

Theoretical Study of Electrochemical and Electrochromic Properties of Novel Viologen Derivatives: Effects of Donors and π-Conjugation.

We propose a linkage approach by merging ambipolar electrochromic (EC) materials in both π-acceptor-π (π-A-π) and donor-acceptor-donor (D-A-D) configurations and investigated their electrochemical and spectroelectrochemical properties using density functional theory calculations. Here, we considered anthracene, toluene, and pyrene as π-conjugated molecules, triphenylamine (TPA) as a donor, and viologen as an acceptor moiety for π-A-π and D-A-D configurations. We have also explored the substitutional effects in the donor moiety on the overall electrochromism during both oxidation and reduction processes. Here, we mainly focused on the relationship between the structure, substitution of functional groups, electronic and spectral properties, as well as redox potential of the designed monomers. Our calculations indicate that the designed monomers have attractive absorption properties and show clear color switching upon the redox process. We find that the substitution of stronger electron-donating and π-spacer groups create new absorption peaks in the oxidation states. These designed viologen derivatives will be potential candidates, which can be used in both oxidation and reduction processes for upcoming EC devices.

Effects of the terminal donor unit in dyes with D-D-π-A architecture on the regeneration mechanism in DSSCs: a computational study.

This theoretical study on dye-sensitized solar cells (DSSCs) includes design strategies for dye donor units to improve the efficiency of DSSCs, and further illuminates the organic dye regeneration mechanism. We have designed a series of new organic sensitizers based on a D-D-π-A architecture to exhibit easy electron transfer and to have remarkable light harvesting properties in the visible region by density functional theory (DFT) and time-dependent (TD)-DFT calculations. Furthermore, the interaction of the organic sensitizers with the conventional redox electrolyte using the triiodide/iodide couple (I3-/I-) is investigated. Our calculations indicate that incorporation of strong electron-donating groups remarkably improves the charge transfer characteristics, optoelectronic properties and rapid dye regeneration as compared to less electron donating substituents. In addition, our study demonstrates the possibility of second electron injection from the oxidized dye complex to the semiconductor surface, which further confirms our recently proposed dye regeneration mechanism.

Temperature-programmed desorption studies of NH3 and H2O on the RuO2(110) surface: effects of adsorbate diffusion.

Temperature-programmed desorption (TPD) is one of the most straightforward surface science experiments for the determination of the thermodynamic and kinetic parameters of a reaction. In our previous study (J. Phys. Chem. C, 2013, 117, 6136-6142), we proposed a model combining DFT methods with microkinetics to investigate the TPD spectra of NH3 and H2O on the RuO2(110) surface. Although our model predicted both the physisorption and chemisorption peaks of both adsorbates in agreement with the experimental TPD spectra, it failed to explain the region between the physisorption and chemisorption areas and underestimated the intensity of the adsorbate in these areas. Hence, to improve our model, in this study, we considered the diffusion of adsorbates from the sub-monolayer to the second layer. Accordingly, we simulated the TPD spectra of both NH3 and H2O on the RuO2(110) surface using condensation approximation. Our results indicate that the diffusion barriers of the adsorbates at high coverage are smaller than their direct desorption energies. Hence, the diffusion of the adsorbates to the second layer from the sub-monolayer at higher coverage is kinetically favorable, which then desorb directly even at low temperatures. Furthermore, the simulated TPD spectra clearly depict the previous experimental results of both adsorbates after considering the diffusion.

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.

Spin-polarized transport properties in some transition metal dithiolene complexes.

Spin filtering materials are of great current interest in part due to their applications in molecular electronics. In this study, we carried out a theoretical investigation on the charge transport properties of transition metal (TM) dithiolene complexes with TM = Ni, Fe and Mn by using non-equilibrium Green's function/density functional theory (NEGF-DFT) methods. The characteristics of current-voltage and spin-resolved transmission spectra pointed out that Ni complexes are non-polarized, while Fe and Mn complexes exhibit high polarization and can be regarded as excellent candidates for spin-filtering materials with high spin-filtering efficiency. These differences were rationalized on the basis of electron delocalization over the molecular junction of the partial distribution of α- and ß-spin molecular projected self-consistent Hamiltonian (MPSH) orbitals, and also the first eigenchannels of molecular junctions.