Combined Density Functional Theory Research Articles

Deep insights into the optoelectronic properties of AgCdF3-based perovskite solar cell using the combination of DFT and SCAPS-1D simulation

The main focus of this research is to explore the properties and photovoltaic application of AgCdF3, and hence, initially, the CASTEP software was used in this study to assess the structural, optical, mechanical, and electrical characteristics of the AgCdF3 perovskite absorber layer within the context of the density functional theory (DFT) method. AgCdF3 resulting from the structural research is confirmed to be chemically and thermodynamically stable by the estimated tolerance factor and formation enthalpy. According to the band structure analysis, AgCdF3 is an indirect band gap semiconductor with a band gap of 1.106 eV, where the electrons of Cd-4d and F-2s dominate the band edges of this semiconductor. Analysis of mechanical properties revealed that the AgCdF3 cubic perovskite has a stable structure and enhanced ductility, indicating superior machinability. After completing the DFT analysis, a one-dimensional solar cell capacitance simulator 1D (SCAPS-1D) was used with three popular electron transport layers (ETLs), including ZnO, PCBM, and C60, to examine the photovoltaic (PV) performance of various AgCdF3-based solar cell heterostructures. Based on simulation findings, the device design with ITO/ZnO/AgCdF3/CuI/Au showed the highest photoconversion efficiency compared to the other configurations. A detailed analysis was conducted for the aforementioned configurations to determine the impact of variations in the absorber and ETL thickness on PV performance. Moreover, the effects of the three designs were assessed in terms of function, generation and recombination rate, capacitance, operating temperature, series and shunt resistance, and Mott-Schottky. Thus, this comprehensive simulation with validation results demonstrated the true potential of AgCdF3 absorber with appropriate ETLs such as ZnO, PCBM, and C60; on the other hand, the CuI as hole transport layer (HTL), paving the way for promising studies to develop high-efficiency AgCdF3 PSCs for the photovoltaic industry.

Ni coarsening under humid atmosphere in the electrode of solid oxide cells: A combined study of density-functional theory and phase-field modeling

Ni coarsening in solid oxide cell (SOC) electrodes is known to be significantly faster under a humid atmosphere. The underlying mechanisms, though, have not been fully understood. In this work, we examine the surface diffusion of Ni(OH)x by a combination of density-functional theory and phase-field modeling. Density-functional theory is used to evaluate the adsorption and diffusion of the Ni(OH)x species on Ni (111) surface, and the results are used to obtain the effective surface diffusivity of Ni versus steam and hydrogen gas partial pressures. This diffusivity is used as an input for a phase-field model to investigate the Ni coarsening in SOC electrodes. It is found that Ni(OH)x formed through chemical reaction cannot accelerate coarsening unless an extremely high steam to hydrogen ratio is reached. However, if Ni(OH)x is formed through electrochemical reactions near triple phase boundaries (TPBs), surface diffusion of Ni(OH)x may cause faster Ni coarsening in fuel cell mode under a large overpotential. Specifically, surface diffusion of Ni(OH) may be comparable to or faster than that of Ni under an overpotential that is large but still possible under fuel cell operating conditions.

Boosting BaTi4O9 photocatalytic H2 evolution activity by functionalized CuNi alloy

H2 evolution through photocatalysis possesses has the advantage for achieving the carbon neutral, that relies on the highly efficient catalysts. Non-noble metals have lower prices than noble metals, which is beneficial for their large-scale applications in industry. In this paper, functionalized CuNi alloy and BaTi4O9 (BTO) composite (CuxNiy/BTO(Z)) photocatalyst were synthesized successfully through hydrothermal calcination method. The acetates were selected the raw material to avoid the use of hazardous chemicals and pollution of photocatalysts by other elements, while also providing C=O for the photocatalyst to further enhance its photocatalytic activity. Under visible light irradiation, the photocatalytic hydrogen (H2) evolution rate of Cu3Ni/BTO is 184.14 μmol·g−1·h−1, which is 101.18 times that of pure BTO (1.82 μmol·g−1·h−1) under the same conditions. Combining density functional theory (DFT) calculations and experimental studies, it is concluded that electronic structural characteristics of BaTi4O9 and the addition of CuNi alloy could provide more electrons and improve the photocatalytic H2 evolution activity.

New insight on the sources of p-type conductivity in SnO

The precise explanation for the p-type characteristics of SnO at a microscopic level remains unclear. However, understanding SnO conduction behavior is critical for optimizing SnO-based p-type transparent conducting. Through a combination of Density Functional Theory (DFT) and Nuclear Magnetic Resonance (NMR) analyses, we have discovered that the p-type properties of SnO arise from the existence of these extra holes in the dispersive Bloch-like band formed by Sn2+-O2-Sn4+ complexes. We hope that our findings will aid in the development of highly efficient SnO-based technology.

In Situ Tracking of Water Oxidation Generated Nanoscale Dynamics in Layered Double Hydroxides Nanosheets.

Layered double hydroxides (LDHs) are potential catalysts for water oxidation, and it is recognized that they undergo dynamic evolution during the operation. However, little is known about the interfacial behaviors at the nanoscale under working conditions nor the underlying effects on electrocatalytic performance. Herein, using electrochemical atomic force microscopy, we in situ visualize the heterogeneous evolution of LDH nanosheets during oxygen evolution reaction (OER). By further combining density functional theory calculations, we elucidate the origin of the heterogeneous dynamics and their impact on the OER efficiency. Our findings demonstrate that NiCo LDHs transform to the catalytically active NiCoOx(OH)2-x phase during OER, and the redox transition between is accompanied by compressive and tensile strain, leading to in-plane contraction and reversible expansion of the nanosheets. Nonisotropic strain and out-of-plane strain relaxation due to defects and interparticle interactions result in cracking and wrinkling in the nanostructure, which is responsible for the partial activation and long-term deterioration of LDH electrocatalysts toward the OER. With this knowledge, we suggest and validate that engineering defects can precisely tune these dynamic behaviors, improving the OER activity and stability among LDH-based electrocatalysts.

Quenching and enhancement mechanisms of a novel Cd-based coordination polymer as a multiresponsive fluorescent sensor for nitrobenzene and aniline

BackgroundNitroaromatic compounds are inherently hazardous and explosive, so convenient and rapid detection strategies are needed for the sake of human health and the environment. There is an urgent demand for chemical sensing materials that offer high sensitivity, operational simplicity, and recognizability to effectively monitor nitroaromatic residues in industrial wastewater. Despite its importance, the mechanisms underlying fluorescence quenching or enhancement in fluorescent sensing materials have not been extensively researched. The design and synthesis of multiresponsive fluorescent sensing materials have been a great challenge until now. ResultsIn this study, a one-dimensional Cd-based fluorescent porous coordination polymer (Cd–CIP-1) was synthesized using 5-(4-cyanobenzyl)isophthalic acid (5-H2CIP) and 4,4′-bis(1-imidazolyl)biphenyl (4,4′-bimp) and used for the selective detection of nitrobenzene in aqueous solution by fluorescence quenching, with a limit of detection of 1.38 × 10−8 mol L−1. The presence of aniline in the Cd–CIP-1 solution leads to the enhancement of fluorescence property. Density functional theory and time-dependent density functional theory calculations were carried out to elucidate the mechanisms of the fluorescence changes. This study revealed that the specific pore size of Cd–CIP-1 facilitates analyte screening and enhances host-guest electron coupling. Furthermore, π–π interactions and hydrogen bond between Cd–CIP-1 and the analytes result in intermolecular orbital overlap and thereby boosting electron transfer efficiency. The different electron flow directions in NB@Cd–CIP-1 and ANI@Cd–CIP-1 lead to fluorescence quenching and enhancement. Significance and noveltyThe multiresponsive coordination polymer (Cd–CIP-1) can selectively detect nitrobenzene and recognize aniline in aqueous solutions. The mechanism of fluorescence quenching and enhancement has been thoroughly elucidated through a combination of density functional theory and experimental approaches. This study presents a promising strategy for the practical implementation of a multiresponsive fluorescent chemical sensor.

Remarkably high tensile strength and lattice thermal conductivity in wide band gap oxidized holey graphene C2O nanosheet

Recently, the synthesis of oxidized holey graphene with the chemical formula C2O has been reported (J. Am. Chem. Soc. 2024, 146, 4532). We herein employed a combination of density functional theory (DFT) and machine learning interatomic potential (MLIP) calculations to investigate the electronic, optical, mechanical and thermal properties of the C2O monolayer, and compared our findings with those of its C2N counterpart. Our analysis shows that while the C2N monolayer exhibits delocalized π-conjugation and shows a 2.47 eV direct-gap semiconducting behavior, the C2O counterpart exhibits an indirect gap of 3.47 eV. We found that while the C2N monolayer exhibits strong absorption in the visible spectrum, the initial absorption peaks in the C2O lattice occur at around 5 eV, falling within the UV spectrum. Notably, we found that the C2O nanosheet presents significantly higher tensile strength compared to its C2N counterpart. MLIP-based calculations show that at room temperature, the C2O nanosheet can exhibit remarkably high tensile strength and lattice thermal conductivity of 42 GPa and 129 W/mK, respectively. The combined insights from DFT and MLIP-based results provide a comprehensive understanding of the electronic and optical properties of C2O nanosheets, suggesting them as mechanically robust and highly thermally conductive wide bandgap semiconductors.

A DFT/MRCI Hamiltonian parameterized using only ab initio data: I. valence excited states

A new combined density functional theory and multi-reference configuration interaction (DFT/MRCI) Hamiltonian parameterized solely using the benchmark ab initio vertical excitation energies obtained from the QUEST databases is presented. This new formulation differs from all previous versions of the method in that the choice of the underlying exchange–correlation (XC) functional employed to construct the one-particle (orbital) basis is considered, and a new XC functional, QTP17, is chosen for its ability to generate a balanced description of core and valence vertical excitation energies. The ability of the new DFT/MRCI Hamiltonian, termed QE8, to furnish accurate excitation energies is confirmed using benchmark quantum chemistry computations, and a mean absolute error of 0.16 eV is determined for the wide range of electronic excitations included in the validation dataset. In particular, the QE8 Hamiltonian dramatically improves the performance of DFT/MRCI for doubly excited states. The performance of fast approximate DFT/MRCI methods, p-DFT/MRCI and DFT/MRCI(2), is also evaluated using the QE8 Hamiltonian, and they are found to yield excitation energies in quantitative agreement with the parent DFT/MRCI method, with the two methods exhibiting a mean difference of 0.01 eV with respect to DFT/MRCI over the entire benchmark set.

Insights into the removal of volatile organic compounds by three-dimensional ordered microporous zeolite-templated carbon: A combined experimental study and density functional theory calculation

Volatile organic compounds (VOCs) threaten human health and the ecological environment, requiring to be removed timely. Zeolite-templated carbon with and without sulfur (ZTC and S-doped ZTC) was prepared by the chemical vapor deposition (CVD) method in a rotating bed reactor and used to remove VOCs. ZTC samples showed narrow and ordered microporous structure (0–2 nm), high specific surface area (2049.05–1732.06 m2/g), abundant pore volume (1.28 – 1.16 cm3/g), and uniform sulfur distribution (S-doped ZTC). Afterwards, the VOCs adsorption capacity was tested at 30, 60, and 90 °C. The results showed that S-doped ZTC exhibited higher benzene (138.2 mg/g) and toluene (171.8 mg/g) adsorption capacities at 30 °C than those performed at 60 and 90 °C owing to the exothermic process. Moreover, S-doped ZTC showed better VOCs adsorption capacity than ZTC-RC due to the combination of physical and weak chemical adsorption. Subsequently, S-doped ZTC captured more toluene (171.8 mg/g) than benzene (138.2 mg/g) because of the dipole–dipole interaction. Furthermore, Fourier transform infrared spectrum (FTIR) and density functional theory (DFT) calculation revealed that inorganic components (NH3, NO, and SO2) imposed a negative effect on VOCs adsorption due to the comparative adsorption. This study offered insights into how ZTC structure and sulfur modification affected the adsorption of VOCs, providing a reliable guideline for the preparation and utilization of adsorbents used to remove VOCs.

New perspective on the electrodeposition of Pb, Cd and Zn in electrode modified with bismuth film: A theoretical–experimental approach

Understanding electrode-analyte interactions at the atomic level is vital for improving analytical techniques, yet the complexity of these interactions poses a significant challenge for refinement.In this study, we investigate the detection of transition metals using Bi film electrodes, combining Density Functional Theory (DFT) simulations with experimental Anodic Stripping Voltammetry (ASV). Our experiments focus on the electrodeposition and detection of Zn2+, Cd2+, and Pb2+using Bi-modified carbon electrodes. The ASV experiments reveal a notably higher sensitivity for Pb2+detection compared to Zn2+and Cd2+, whether evaluated individually or simultaneously. DFT calculations demonstrate that the higher adsorption energy of Pb on the Bi surface promotes a uniform distribution of Pb atoms, resulting in a homogeneous phase. Conversely, Cd and Zn tend to present lower adsorption energies and form metallic clusters, leading to phase segregation. The correlation between theoretical and experimental data suggests that a more uniform deposition of Pb on the electrode surface facilitates a regular sweep in the redissolution step, achieving a detection limit as low as 0.062 nM for Pb. This synergistic approach not only enhances our understanding of electrode-analyte interactions but also provides valuable insights for optimizing electrode materials and detection methodologies in analytical chemistry.

Axial Coordinated Manganese(III) Porphyrin/Tetraazaporphyrin - 4-(10-phenylanthracen-9-yl)Pyridine Dyads: Self-Assembly, Structure and Spectral Properties in Ground and Excited States.

Self-assembly of new donor-acceptor systems based on (5,10,15,20-tetraphenylporphinato)manganese(III)/(5,10,15,20-tetra-4-tert-butylphenylporphinato)manganese(III)/(octakis(4-tert-butylphenyl)tetraazaporphinato)manganese(III) acetate ((AcO)MnTPP/(AcO)MnTBPP/(AcO)MnTAP) and 4-(10-phenylanthracen-9-yl)pyridine (PyAn) was studied using fluorescence spectroscopy and mass spectrometry. It was found that the coordination complexes of 1 : 1 composition (dyads) are formed in toluene. The spectral properties, the chemical structures and redox behavior of the dyads were described using 1H NMR, IR, ESR spectroscopy and cyclic voltammetry, respectively. The dynamic processes and the characteristics in the excited state of the dyads were obtained using the femtosecond transient absorption spectroscopy method. Density functional theory (DFT), time-dependent DFT methods were used to elucidate the dyad electronic structures and to establish the differences in their frontier molecular orbitals. The analysis of the lambda parameter and the distance of hole-pair interaction was indicated more favorable charge transfer between the macrocycle and the axial PyAn fragment in (AcO)(PyAn)MnTAP. The calculated values of the zero-field splitting parameters D and E/D, together with the g tensors of the lowest spin-orbit state for (AcO)MnTPP and (AcO)(PyAn)MnTPP were obtained using the combination of DFT and Multireference Perturbation Theory (CASSCF/NEVPT2) simulations. The data obtained develop the fundamental basis in the field of photovoltaics and show the prospects for the study of molecular systems of this class.

On the CO2 Harvesting from N2 Using Grazyne Membranes.

The separation of carbon dioxide (CO2) from nitrogen (N2) is at the core of any global warming remediation technology aimed at reducing the CO2 content in the atmosphere. Chemical membranes designed to differentially permeate both molecules have become quite appealing due to their simple use, although many membrane-based separations stand out as a promising solution for CO2 separation. These are environmentally friendly, with high active surface areas, compact design, easy to maintain and cost-effective, although the field is still growing due to the difficulties in the CO2/N2 separation. The present study poses grazynes, two-dimensional C-based materials with sp and sp2 C atoms, aligned along stripes, as suited membranes for the CO2/N2 separation. The combination of density functional theory (DFT) and molecular dynamics (MD) simulations allow tackling the energetics, kinetics, and dynamics of the membrane effectiveness of grazynes with engineered pores for such a separation in a holistic fashion. The explored grazynes are capable of physisorbing CO2 and N2, thus avoiding material poisoning by molecular decoration, while the diffusion of CO2 through the pores is found to be rapid, yet easier than that of N2, in the rate order of the s-1 in the 100-500 K temperature range. In particular, low-temperature CO2 separation even for CO2 contents below 0.5 % are found for [1],[2]{2}-grazyne when controlling the membrane exposure contact to the gas mixture, paving the way for exploring and using grazynes for air CO2 remediation.

Emergence of a potential charge-disproportionated insulating state in SrCrO3

We use a combination of density functional theory (DFT) and dynamical mean-field theory (DMFT) to investigate the potential emergence of a charge-disproportionated insulating phase in SrCrO3, whereby the Cr cations disproportionate according to 3Cr4+→2Cr3++Cr6+ and arrange in ordered planes perpendicular to the cubic [111] direction. We show that the charge disproportionation couples to a structural distortion where the oxygen octahedra around the nominal Cr6+ sites contract, while the octahedra surrounding the Cr3+ sites expand and distort. Our results indicate that the charge-disproportionated phase can be stabilized for realistic values of the Hubbard U and Hund's J parameters, but this requires a scaling of the DFT+DMFT double-counting correction by at least 35%. The disproportionated state can also be stabilized in DFT+U calculations for a specific magnetic configuration with antiparallel magnetic moments on adjacent Cr3+ sites and no magnetic moment on the Cr6+ sites. While this phase is higher in energy than other magnetic states that can arise in SrCrO3, the presence of an energy minimum suggests that the charge-disproportionated state represents a metastable state of SrCrO3. Published by the American Physical Society 2024

Cu inanchored MnO/carbonaceous frameworks trigger peroxymonosulfate activation for enrofloxacin degradation: ROS generation and pollutant attacking processes

Despite Fluoroquinolone antibiotics (FQs) removal in peroxymonosulfate (PMS) activation have been widely researched and the outstanding degradation performance have been gained, the detailed processes by which reactive oxygen species attack pollutants have not been adequately studied. In this study, a Cu/MnO catalyst is anchored onto carbonaceous frameworks using a one-step calcination method for investigation. Benefiting from the sp2 unsaturated carbon as well as the synergistic effect between Cu2+/Cu+/Cu and Mn3+/Mn2+ bimetallic redox electron pairs, the prepared Cu/MnO anchored on carbonaceous frameworks catalyst (4CuMn/C-800) material possesses excellent enrofloxacin (ENR) removal performance, where 85.52 % of ENR is degraded in 80 mins, and maintains relatively high catalysis performance even in the various reaction conditions (reaction pH, reaction temperature, existing anions etc.). The analysis reveals the 1O2 and •O2-, as the dominate ROS, continuously attack the specific active sites of ENR molecules until they are mineralized. In detail, the generated •O2- mainly attacks the piperazine ring, while the formed 1O2 assaults the quinolone group of ENR. By combining density functional theory (DFT) calculations with LC-MS analysis, we propose four distinct pathways for ENR degradation in the 4CuMn/C-800/PMS system. In summary, this study offers a novel and practical approach to design metal/metal oxide/carbon catalysts and enhances our understanding of the mechanisms behind ROS-driven PMS activation.

Adsorption differences of xanthate, dithiophosphate and dithiocarbamate on stibnite (010) surface with Cu2+ activated: Combined DFT calculations and experiments

Antimony is an important strategic metal resource. Stibnite as one of the main sources of antimony resources, efficiently recycling stibnite has always been a topic of interest. Currently, there is a scarcity of research examining the adsorption differences of butyl xanthate (BX), sodium diethyldithiocarbamate (DDTC) and ammonium dibutyl dithiophosphate (ADD) on the stibnite (010) surface with Cu2+ activated based on atomic scale. This study investigates the adsorption differences of BX, DDTC and ADD on the stibnite (010) surface with Cu2+ activated, combining density functional theory with experiments. DFT calculations showed that there are five adsorption sites of Cu2+ on the stibnite surface, analysis of partial density of states (PDOS) indicated that the difference in hybridization strength between Cu 3d and S 3p orbitals caused discrepancy in adsorption sites performance. Analysis of PDOS, Mulliken population and electron density difference, it can be concluded that the collector interaction strongly with the stibnite surface with Cu2+ activated and the difference of charge transferred by S atoms during the interaction process is the main reason for the differences in adsorption performance and the varying stability of CuS bonds in adsorption models. Under comprehensive comparison the flotation experiments and adsorption tests showed that with Cu2+ activation, the recovery rate of stibnite was significantly improved with DDTC and the adsorption effect was optimal. Finally, the adsorption performance sequence on Cu2+ activated stibnite surface for the three collectors is as follows: DDTC > ADD > BX. This study combining experimental and DFT calculations, provides guidance for the development of efficient collectors for stibnite flotation in the future.

Goldene: An Anisotropic Metallic Monolayer with Remarkable Stability and Rigidity and Low Lattice Thermal Conductivity.

In a recent breakthrough in the field of two-dimensional (2D) nanomaterials, the first synthesis of a single-atom-thick gold lattice of goldene has been reported through an innovative wet chemical removal of Ti3C2 from the layered Ti3AuC2. Inspired by this advancement, in this communication and for the first time, a comprehensive first-principles investigation using a combination of density functional theory (DFT) and machine learning interatomic potential (MLIP) calculations has been conducted to delve into the stability, electronic, mechanical and thermal properties of the single-layer and free-standing goldene. The presented results confirm thermal stability at 700 K as well as remarkable dynamical stability of the stress-free and strained goldene monolayer. At the ground state, the elastic modulus and tensile strength of the goldene monolayer are predicted to be over 226 and 12 GPa, respectively. Through validated MLIP-based molecular dynamics calculations, it is found that at room temperature, the goldene nanosheet can exhibit anisotropic tensile strength over 9 GPa and a low lattice thermal conductivity around 10 ± 2 W/(m.K), respectively. We finally show that the native metallic nature of the goldene monolayer stays intact under large tensile strains. The combined insights from DFT and MLIP-based results provide a comprehensive understanding of the stability, mechanical, thermal and electronic properties of goldene nanosheets.

Interplay of altermagnetism and weak ferromagnetism in two-dimensional RuF4

Gaining growing attention in spintronics is a class of magnets displaying zero net magnetization and spin-split electronic bands called altermagnets. Here, by combining density functional theory and symmetry analysis, we show that RuF4 monolayer is a two-dimensional (2D) d-wave altermagnet. Spin–orbit coupling leads to pronounced spin splitting of the electronic bands at the Γ point by ∼100meV and turns the RuF4 into a weak ferromagnet due to nontrivial spin-momentum locking that cants the Ru magnetic moments. The net magnetic moment scales linearly with the spin–orbit coupling strength. Using group theory we derive an effective spin Hamiltonian capturing the spin-splitting and spin-momentum locking of the electronic bands. Disentanglement of the altermagnetic and spin–orbit coupling induced spin splitting uncovers to which extent the altermagnetic properties are affected by the spin–orbit coupling. Our results move the spotlight to the nontrivial spin-momentum locking and weak ferromagnetism in the 2D altermagnets relevant for novel venues in this emerging field of material science research.

High-Entropy Alloy Electrocatalysts Bidirectionally Promote Lithium Polysulfide Conversions for Long-Cycle-Life Lithium-Sulfur Batteries.

High-entropy alloys (HEAs) have attracted considerable attention, owing to their exceptional characteristics and high configurational entropy. Recent findings demonstrated that incorporating HEAs into sulfur cathodes can alleviate the shuttling effect of lithium polysulfides (LiPSs) and accelerate their redox reactions. Herein, we synthesized nano Pt0.25Cu0.25Fe0.15Co0.15Ni0.2 HEAs on hollow carbons (HCs; denoted as HEA/HC) by a facile pyrolysis strategy. The HEA/HC nanostructures were further integrated into hypha carbon nanobelts (HCNBs). The solid-solution phase formed by the uniform mixture of the five metal elements, i.e., Pt0.25Cu0.25Fe0.15Co0.15Ni0.2 HEAs, gave rise to a strong interaction between neighboring atoms in different metals, resulting in their adsorption energy transformation across a wide, multipeak, and nearly continuous spectrum. Meanwhile, the HEAs exhibited numerous active sites on their surface, which is beneficial to catalyzing the cascade conversion of LiPSs. Combining density functional theory (DFT) calculations with detailed experimental investigations, the prepared HEAs bidirectionally catalyze the cascade reactions of LiPSs and boost their conversion reaction rates. S/HEA@HC/HCNB cathodes achieved a low 0.034% decay rate for 2000 cycles at 1.0 C. Notably, the S/HEA@HC/HCNB cathode delivered a high initial areal capacity of 10.2 mAh cm-2 with a sulfur loading of 9 mg cm-2 at 0.1 C. The assembled pouch cell exhibited a capacity of 1077.9 mAh g-1 at the first discharge at 0.1 C. The capacity declined to 71.3% after 43 cycles at 0.1 C. In this work, we propose to utilize HEAs as catalysts not only to improve the cycling stability of lithium-sulfur batteries, but also to promote HEAs in energy storage applications.

Synergistic effect of amino and hydroxyl bifunctional modified h-BN on interfacial thermal conductivity in polydimethylsiloxane matrix: Simulations and experiments

As a widely used thermal conductive matrix material, the interface problem between polydimethylsiloxane (PDMS) and thermal conductive fillers needs to be solved urgently. The interfacial heat transfer mechanism between PDMS and hexagonal boron nitride (h-BN) modified by different groups was studied by combining density functional theory (DFT) simulation and molecular dynamics (MD) simulation. The bi-functionalization of h-BN was achieved by the environmentally friendly 6-aminocaproic acid (ACA) additive-assisted water ball milling process. The h-BN/PDMS composite thermal interface materials were prepared using a simple rolling method. The thermal conductivity of the obtained sample reached 1.256 W m−1 K−1 at a filler loading of 15 wt%. The proposed bifunctional synergistic heat transfer mechanism is expected to provide theoretical guidance for the preparation of high thermal conductivity and insulating PDMS used in electronic communications.

Optimization of Lithium Metal Anode Performance: Investigating the Interfacial Dynamics and Reductive Mechanism of Asymmetric Sulfonylimide Salts

Asymmetric lithium salts, such as lithium (difluoromethanesulfonyl)(trifluoromethanesulfonyl)imide (LiDFTFSI), have been demonstrated to surpass traditional symmetric lithium salts with improved Li+ conductivity and the capacity to generate a stable solid electrolyte interphase (SEI) while maintaining compatibility with an aluminum (Al0) current collector. However, the intrinsic reductive mechanism through which LiDFTFSI influences battery performance remains unclear and under debate. Herein, detailed SEI reactions of LiDFTFSI–based electrolytes were investigated by combining density functional theory and molecular dynamics, aiming to clarify the formation process and atomic structure of the SEI. Our results show that asymmetric DFTFSI− weakens the interaction between carbonate solvents and Li+, and substantially alters the solvation structure, exhibiting a well-balanced coordination capacity compared to bis(trifluoromethanesulfonyl)imide (TFSI−). Nanosecond hybrid molecular dynamics simulation further reveals that preferential decomposition of LiDFTFSI produces sufficient LiF and Li2O to facilitate a robust SEI. Moreover, abundant F− generated from LiDFTFSI decomposition accumulates on the Al surface and subsequently combines with Al3+ from the current collector to form AlF3, potentially inhibiting corrosion of the current collector. Overall, these findings elucidate how LiDFTFSI regulates the solvation sheath and SEI structure, advancing the development of high-performance electrolytes compatible with current collectors.