Density Functional Molecular Dynamics Research Articles

The nucleation mechanism of MoS2 on Au(111) surface

Controllable preparation of two-dimensional MoS2 single crystal thin films is the key to its development and application. Chemical vapor deposition (CVD) is considered one of the most promising methods for large-scale production of 2D MoS2 films. However, at present, the single crystal MoS2 films prepared by CVD have defects and insufficient sizes. The reason may be that the CVD growth mechanism of MoS2 is still unclear. In this paper, density functional theory (DFT) and molecular dynamics (MD) simulations are used to systematically explore the nucleation mechanism of MoS2 grown on Au (111) surface with molybdenum powder and H2S as precursors. In our theoretical study, some key links of MoS2 nucleation have been clearly displayed, such as deposition of molybdenum, dehydrogenation of H2S, lifting of Mo atoms and so on. This study provides a deep understanding of the nucleation of MoS2 during CVD growth and theoretical basis for the synthesis of various TMDs.

Weakly Hydrated Solute of Mixed Hydrophobic-Hydrophilic Nature.

Infrared (IR) spectroscopy is a commonly used and invaluable tool in studies of solvation phenomena in aqueous solutions. Concurrently, density functional theory calculations and ab initio molecular dynamics simulations deliver the solvation shell picture at the molecular detail level. The mentioned techniques allowed us to gain insights into the structure and energy of the hydrogen bonding network of water molecules around methylsulfonylmethane (MSM). In the hydration sphere of MSM, there are two types of populations of water molecules: a significant share of water molecules weakly bonded to the sulfone group and a smaller share of water molecules strongly bonded to each other around the methyl groups of MSM. The very weak hydrogen bond of water molecules with the hydrophilic group causes the extended network of water hydrogen bonds to be not "anchored" on the sulfone group, and consequently, the MSM hydration shell is labile.

Citrullus colocynthis fruit extract as effective eco-friendly corrosion inhibitor in a hydrochloric acid pickling medium for carbon steel by using both experimental and theoretical studies.

The present study focuses on an environmental approach based on the use of an eco-friendly corrosion inhibitor from the Citrullus colocynthis fruit extract for enhancement corrosion resistance of carbon steel (C-S) in acid medium as an alternative to various organic and non-organic chemical inhibitors. The evaluation of the inhibition properties of the fruit methanolic extract of Citrullus colocynthis (CCE) were performed in molar hydrochloric acid (1M HCl) medium using gravimetric and electrochemical (potentiodynamic polarization and AC impedance) techniques as well as surface analyses. CCE is rich in amino acids, mainly citrulline and β-(pyrazo-1-yl)-L-analine molecules. Based on the weight loss evaluation, the results demonstrated that this plant extract acts as an effective corrosion inhibitor and a protection level of 93.6% was attained at 500ppm of CCE after 6h of metal exposure at 303K. According to polarization curves, CCE functions as a mixed-type inhibitor. In addition, AC impedance analyses have shown that the incorporation of CCE into the corrosive solution leads to a decrease in load capacity, while improving the charge/discharge function at the interface. This suggests the possibility of the formation of an adsorbed layer on the C-S surface. In addition, scanning electron microscope (SEM) observation, contact angle measurements, and Fourier-transform infrared spectroscopy (FTIR) analyses supported the development of a protective film over CS substrate surface afterwards addition of CCE. Langmuir and/or Temkin isotherms can be used to characterize the adsorption of this organic inhibitor on the C-S surface. X-ray photoelectron spectroscopy (XPS) has revealed that the inhibiting effect of CCE on the corrosion of C-S in 1M HCl solution is mainly controlled by a chemisorption process and the inhibitive layer is composed of an iron oxide/hydroxide mixture where CCE molecules are incorporated. In order to understand the relationship between the molecular structure and anti-corrosion effectiveness of these inhibitor molecules, quantum chemical studies were carried out using density functional theory (DFT) and molecular dynamics (MD) simulation.

Physisorption or chemisorption: Insight from AI computing model based on DFT, MC/MD-simulation for prediction of MOF-based inhibitor adsorption on Cu in brine solution

This study investigates the dynamics of cerium metal organic framework (Ce-MOF) adsorption on the Cu surface in brine solution. This research integrates computational modelling based on Density Functional Theory (DFT), Monte Carlo (MC), and Molecular Dynamics (MD) simulations for enhanced predictive modelling. Additionally, by the utilization of the Dmol3 module within Biovia materials studio software, DFT calculations /geometric configurations through the Double Numerical plus d-functions (DND) were achieved. Notably, the results demonstrate a robust negative adsorption energy (−363.54 kcal/mol), indicating a highly stable interaction leading to the formation of a protective film on the metal surface. The study also proposes a corrosion inhibition mechanism involving physical and chemical barriers. The findings not only contribute to fundamental corrosion science but also propose innovative strategies for designing MOF-based inhibitors tailored to specific environmental conditions. This research introduces a novel perspective by combining theoretical calculations, and simulation models for predicting inhibitor behavior, fostering advancements in corrosion protection strategies.

Reversible phase transformations between Pb nanocrystals and a viscous liquid-like phase.

Phase transformations have been a prominent topic of study for both fundamental and applied science. Solid-liquid reaction-induced phase transformations can be hard to characterize, and the transformation mechanisms are often not fully understood. Here, we report reversible phase transformations between a metal (Pb) nanocrystal and a viscous liquid-like phase unveiled by in situ liquid cell transmission electron microscopy. The reversible phase transformations are obtained by modulating the electron current density (between 1000 and 3000 electrons Å-2 s-1). The metal-organic viscous liquid-like phase exhibits short-range ordering with a preferred Pb-Pb distance of 0.5 nm. Assisted by density functional theory and molecular dynamics calculations, we show that the viscous liquid-like phase results from the reactions of Pb with the CH3O fragments from the triethylene glycol solution under electron beam irradiation. Such reversible phase transformations may find broad implementations.

Probing the interaction mechanism of choline chloride-based deep eutectic solvents with flavonoid and polyphenol systems

Choline chloride-based deep eutectic solvents (DES) have been demonstrated as promising green solvents for the extraction of flavonoids and polyphenols. This study investigates the interaction between six different hydrogen bond donors (HBD) choline chloride-based DES and three types of polyphenolic flavonoid substrates. Density functional theory (DFT) and molecular dynamics (MD) simulations suggest that Cl− dominates the interaction primarily through electrostatic forces. The extraction effect of alcohol DES on rutin was optimized obviously, and the maximum interaction could reach 737.6 kJ/mol. Acid DES has a better extraction effect on anthocyanins, with a maximum interaction of 376.4 kJ/mol. With the increase of the carbon chain of HBA and the increase of the number of functional groups, the interaction between DES and the active substance decreases. As HBD, ethanolamine with both hydroxyl and amino groups showed the best effect in the extraction process of DES, forming the maximum interaction energy of 1575.8 kJ/mol. Additionally, multivariate analysis is employed to establish the relationship between different variables and interaction energy. This study provides micro-theoretical support for the extraction of flavonoids and polyphenols.

Understanding the phase stability in a multi-principal-component AlCuFeMn alloy

Method(s) that can reliably predict phase evolution across thermodynamic parameter space, especially in complex systems, are of critical significance in academia as well as in the manufacturing industry. In the present work, the phase stability in an equimolar AlCuFeMn multi-principal-component alloy (MPCA) was predicted using complementary first-principles density functional theory calculations and ab initio molecular dynamics (AIMD) simulations. The temperature evolution of completely disordered, partially ordered, and completely ordered phases was examined based on the Gibbs free energy. Configurational, electronic, vibrational, and lattice mismatch entropies were considered to compute the Gibbs free energy of the competing phases. Additionally, elemental segregation was studied using AIMD. The predicted results at 300 K align well with room-temperature experimental observations using x-ray diffraction and scanning and transmission electron microscopy on a sample prepared using commercially available pure elements. The adopted method could help in predicting plausible phases in other MPCA systems with complex phase stability.

Unraveling the corrosion inhibition behavior of prinivil drug on mild steel in 1M HCl corrosive solution: insights from density functional theory, molecular dynamics, and experimental approaches.

The deterioration of mild steel in an acidic environment poses a significant challenge in various industries. The emergence of effective corrosion inhibitors has drawn attention to studies aimed at reducing the harmful consequences of corrosion. In this study, the corrosion inhibition efficiency of Prinivil in a 1M HCl solution through various electrochemical and gravimetric techniques has been investigated for the first time. The results demonstrated that the inhibition efficiency of Prinivil expanded from 61.37% at 50ppm to 97.35% at 500ppm concentration at 298K. With a regression coefficient (R 2) of 0.987, Kads value of 0.935 and Ea value of 43.024kJ/mol at 500ppm concentration of inhibitor, a strong affinity of Prinivil for adsorption onto the metal surface has been significantly found. Scanning electron microscopy (SEM) and contact angle measurement analyses further support the inhibitory behavior of Prinivil, demonstrating the production of a defensive layer on the surface of mild steel. Additionally, molecular dynamics (MD) and Monte Carlo simulations were employed to investigate the stability and interactions between Prinivil and the metallic surface (Fe (1 1 0)) at the atomic level. The computed results reveal strong adsorption of Prinivil upon the steel surface, confirming its viability as a corrosion inhibitor.

BF2 complexes of pyridyl‐isoindoline‐1‐ones as an efficient corrosion inhibitor for mild steel in 1 M HCl and the application for surgical instruments anticorrosion

AbstractIn this study, BF2 complexes of pyridyl‐isoindoline‐1‐ones (BPIO) has been firstly designed and investigated as an excellent corrosion inhibitor for the mild steel in 1 M HCl. The corrosion protection properties of BPIO were studied by using a series of experiments. The results indicated BPIO has excellent inhibition performance, and inhibition efficiency of BPIO reached up to 96.6%. The effects of immersion temperature and time were investigated by weight loss experiments to evaluate the stability of adsorbed BPIO film in protecting steel surface. Based on potentiodynamic polarization studies, BPIO acted as one mixed‐type corrosion inhibitor with predominant anodic effectiveness, and its adsorption on the mild steel follows the Langmuir adsorption isotherm. The values of ΔGads suggested the adsorption of BPIO on the mild steel surface was through a combination of chemisorption and physisorption. The adsorption of BPIO molecules on the steel surface was further identified by the techniques of scanning electron microscopy (SEM) and X‐ray photoelectron spectroscopy (XPS). The quantum chemical calculations based on density functional theory (DFT) and molecular dynamics (MD) simulations were used to optimize the BPIO molecular structure and investigate the inhibitive properties on the theoretical level, which agreed well with the experimental results. Besides, BPIO has been used for the development of water soluble metal antirusting agent.

X-functionalized molybdenene monolayers (X = O, F, Al, Si, Cl)

Molybdenene synthesized experimentally is the sole Dirac material with metallic properties so far [Sahu et al., Nat. Nanotechnol. 18, 1430 (2023)], exhibiting a wide array of unique and outstanding properties with potentially extensive applications. However, the free-standing molybdenene structure is not so stable, which highly limits its further exploitation. In this work, we employ density functional theory calculations and ab initio molecular dynamics simulations to investigate molybdenene monolayers functionalized with various elements (X = H, Li, Be, B, C, N, O, F, Na, Mg, Al, Si, P, S, Cl) at both basal surfaces, aiming at achieving the stable free-standing molybdenene derivatives. By evaluating the energetic, mechanical, dynamical, and thermodynamic properties, we confirm some stable monolayer structures of X-functionalized molybdenene (X = O, F, Al, Si, Cl), which are named as X-Molybdenene. Therefore, our findings stabilize the molybdenene via surface functionalization, which is crucial for future experimental validations and applications.

Investigation of branched sulfonated polyimide membranes containing self-synthesized trianhydride monomer for vanadium flow battery via a combined theoretical-experimental strategy

In this work, a new branched trianhydride monomer 1,3,5-tris(4-naphthyloxy-1,8-diacid) phthalic anhydride is established for improving the chemical/dimensional stability and proton conduction of the branched sulfonated polyimide (BSPI) membrane for application in vanadium flow battery (VFB). Compared with linear SPI-60 membrane containing conventional dianhydride monomer 1,4,5,8-naphthalenetetra-carboxylic dianhydride, BSPI-60 membrane exhibits remarkable resistance to vanadium ions, proton conduction and structural stability. Besides, the challenge of simultaneously improving vanadium ions resistance and proton conductance is tackled. The proton selectivity of BSPI-60 membrane achieves 1.11 × 105 S·min/cm3, which is 2.8 and 2.5 times higher than both SPI-60 (0.39 × 105 S·min/cm3) and commercial Nafion 212 (0.44 × 105 S·min/cm3) membranes, respectively. At the same time, BSPI-60 membrane exhibits higher coulomb efficiencies (97.2 %–99.3 %) and energy efficiencies (85.6 %–69.5 %) compared those of SPI-60 and Nafion 212 membranes at 100–300 mA/cm2. Remarkably, the 500 cycles of BSPI-60 membrane at 140 mA/cm2 are also stably executed. The internal reasons for enhanced chemical/dimensional stabilities and proton conduction of BSPI-60 membrane are clarified from theoretical calculations with mean square displacement value, fractional free volume and natural bond orbital charge via density functional theory and molecular dynamics simulation. Our study encompasses not only the synthesis of a novel branched trianhydride monomer but also the development of a BSPI membrane with a unique molecular structure specifically designed for VFB applications.

Uncovering the Aggregation-Induced Emission Mechanisms of Phenoxazine and Phenothiazine Groups.

Molecules with both aggregation-induced emission (AIE) and thermally activated delayed fluorescence (TADF) properties are potential organic light-emitting diode materials; however, the AIE and TADF mechanisms are still debatable. In this work, four molecules incorporating carbazole (Cz), phenoxazine (PXZ), and phenothiazine (PTZ) as donor groups to the diphenylsulfone acceptor were investigated. The experiment results indicate that a molecule containing Cz exhibits solely TADF properties, whereas molecules containing PXZ and PTZ demonstrate both TADF and AIE characteristics. As for DPS-PTZ, the result indicates that the thin-film environment restricts molecular twisting, consequently reducing nonradiative decay, thereby attributing to the AIE property by density functional theory and molecular dynamics simulation. As for DPS-PXZ, the result suggests that the restricted access to a conical intersection in a singlet excited via an expansion in the C-S-C angle is the pivotal factor for the AIE characteristic. The C-S-C angle twist of DPS-PXZ is impeded in the aggregate state and resulted in luminescence. Understanding the mechanisms serves as a valuable guide for the development of new AIE systems, enabling their application in various practical domains.

Carborane-Cluster-Wrapped Copper Cluster with Cyclodextrin-like Cavities for Chiral Recognition.

Chiral atomically precise metal clusters, known for their remarkable chiroptical properties, hold great potential for applications in chirality recognition. However, advancements in this field have been constrained by the limited exploration of host-guest chemistry, involving metal clusters. This study reports the synthesis of a chiral Cu16(C2B10H10S2)8 (denoted as Cu16@CB8, where C2B10H12S2H2 = 9,12-(HS)2-1,2-closo-carborane) cluster by an achiral carboranylthiolate ligand. The chiral R-/S-Cu16@CB8 cluster features chiral cavities reminiscent of cyclodextrins, which are surrounded by carborane clusters, yet they crystallize in a racemate. These cyclodextrin-like cavities demonstrated the specific recognition of amino acids, as indicated by the responsive output of circular dichroism and circularly polarized luminescence signals of Cu16 moieties of the Cu16@CB8 cluster. Notably, a quantitative chiroptical analysis of amino acids in a short time and a concomitant deracemization of Cu16@CB8 were achieved. Density functional tight-binding molecular dynamics simulation and noncovalent interaction analysis further unraveled the great importance of the cavities and binding sites for chiral recognition. Dipeptide, tripeptide, and polypeptide containing the corresponding amino acids (Cys, Arg, or His residues) display the same chiral recognition, showing the generality of this approach. The functional synergy of dual clusters, comprising carborane and metal clusters, is for the first time demonstrated in the Cu16@CB8 cluster, resulting in the valuable quantification of the enantiomeric excess (ee) value of amino acids. This work opens a new avenue for chirality sensors based on chiral metal clusters with unique chiroptical properties and inspires the development of carborane clusters in host-guest chemistry.

Density functional theory and molecular dynamics study on the growth of graphene by chemical vapor deposition on copper substrate

Chemical vapor deposition is an affordable method for producing high-quality graphene. Microscopic defects in graphene grown on copper substrates, such as five- and seven-membered rings, degrade the quality of graphene. Therefore, it is essential to study the growth process and factors affecting the quality of graphene on copper surfaces. In this study, first-principles calculations based on density functional theory show that the four-step dehydrogenation reaction of methane is endothermic, with the energy barrier for the last dehydrogenation step being relatively high. Additionally, CH forms dimers on the copper surface with a lower energy barrier and trimers with a higher energy barrier, indicating that carbon dimers are the primary precursor species for graphene growth in the early stages. Subsequently, in molecular dynamics simulations, the analytical bond-order potential based on quantum mechanics is employed. The results reveal that the growth of graphene on the copper surface involves the diffusion and gradual nucleation of carbon dimers in the early stages, the gradual enlargement of graphene domains in the intermediate stages, and the gradual merging of graphene domain boundaries in the later stages. Moreover, the growth of graphene on the copper substrate follows a self-limiting growth mode. Increasing the deposition interval of carbon atoms and reducing the carbon atom deposition velocity contribute to enhancing the quality of graphene grown on the copper substrate.

Amelioration of protective organic layer using acenaphthene-based inhibitor responsible for excellent anti-corrosion performance: Experimental and computational perspectives

Despite the engineering promise offered by the co-existence of organic substances in protecting vulnerable metallic materials from corrosive environments, the interaction and formation mechanisms that induce the development of new materials with improved structural properties remain less understood. This study investigated the corrosion inhibitory properties of two acenaphthene derivatives, acenaphthylene-1,2‑dione (ACP) and 1,2-dihydroacenaphthylen-1-ol (DCP), as inhibitors for N80 steel in a 15 % HCl solution. The anticorrosive effectiveness of ACP and DCP compounds was evaluated through multiple research methods, including weight loss analysis, electrochemical impedance spectroscopy (EIS), potentiodynamic polarization (PDP), and surface characterization using scanning electron microscopy (SEM). The experimental findings demonstrate that ACP exhibits superior inhibition performance compared to DCP, with an inhibition efficiency of 93.54 % for ACP and 73.12 % for DCP at an optimum concentration of 5 × 10–3 M. EIS data show that the charge transfer resistance increases with higher concentrations of both compounds. PDP results indicate that ACP and DCP act as mixed-type inhibitors without altering the corrosion mechanism. The kinetic parameters of corrosion adsorption follow the Langmuir isotherm, highlighting a competition between physical and chemical interactions. To investigate how the geometric structures resulting from functional groups influence their interaction with the metal surface, theoretical calculations employing density functional theory (DFT), molecular dynamics (MD), and density-functional tight-binding (DFTB) were conducted. These calculations were aimed at gaining insights into the adsorption behavior of ACP and DCP on the metal surface and their interfacial mechanism. The calculations demonstrate that the molecule possessing twin donor atoms along with p-type orbitals of aromatic rings significantly influenced the formation of a protective film with a uniform distribution. This configuration exhibited superior corrosion performance compared to a molecule containing only one hydroxyl group (—OH). Theoretical calculations further suggest that ACP exhibits stronger adsorption ability, with the two oxygen atoms identified as the most reactive sites, indicating their tendency to donate electrons to the iron surface. The robust resonance-stabilized structure of ACP enhances the stability of the molecules, facilitating its interaction and adsorption onto the metal surface compared to the DCP inhibitor. Overall, the superior inhibition performance of ACP is attributed to the close bonding of twin donor fragments within the ACP molecule, forming a more compact adsorbed inhibitor film on the steel surface.

Formation of Supernarrow Borophene Nanoribbons

AbstractBorophenes have sparked considerable interest owing to their fascinating physical characteristics and diverse polymorphism. However, borophene nanoribbons (BNRs) with widths less than 2 nm have not been achieved. Herein, we report the experimental realization of supernarrow BNRs. Combining scanning tunneling microscopy imaging with density functional theory modeling and ab initio molecular dynamics simulations, we demonstrate that, under the applied growth conditions, boron atoms can penetrate the outermost layer of Au(111) and form BNRs composed of a pair of zigzag (2,2) boron rows. The BNRs have a width self‐contained to ∼1 nm and dipoles at the edges to keep them separated. They are embedded in the outermost Au layer and shielded on top by the evacuated Au atoms, free of the need for post‐passivation. Scanning tunneling spectroscopy reveals distinct edge states, primarily attributed to the localized spin at the BNRs’ zigzag edges. This work adds a new member to the boron material family and introduces a new physical feature to borophenes.

Formation of Supernarrow Borophene Nanoribbons.

Borophenes have sparked considerable interest owing to their fascinating physical characteristics and diverse polymorphism. However, borophene nanoribbons (BNRs) with widths less than 2 nm have not been achieved. Herein, we report the experimental realization of supernarrow BNRs. Combining scanning tunneling microscopy imaging with density functional theory modeling and ab initio molecular dynamics simulations, we demonstrate that, under the applied growth conditions, boron atoms can penetrate the outermost layer of Au(111) and form BNRs composed of a pair of zigzag (2,2) boron rows. The BNRs have a width self-contained to ∼1 nm and dipoles at the edges to keep them separated. They are embedded in the outermost Au layer and shielded on top by the evacuated Au atoms, free of the need for post-passivation. Scanning tunneling spectroscopy reveals distinct edge states, primarily attributed to the localized spin at the BNRs' zigzag edges. This work adds a new member to the boron material family and introduces a new physical feature to borophenes.

Revealing the role of interlayer spacing in radioactive-ion sieving of functionalized graphene membranes

Functionalization of graphene enables precise control over interlayer spacing during film formation, thereby enhancing the separation efficiency of radioactive ions in graphene membranes. However, the systematic impact of interlayer spacing of graphene membranes on radioactive-ion separation remains unexplored. This study aims to elucidate how interlayer spacing in functionalized graphene membranes affects the separation of radioactive ions. Utilizing polyamidoxime (PAO) to modify graphene oxide, we controlled the interlayer spacing of graphene membranes. Experimental results indicate that tuning interlayer spacing enables control of the permeation flux of radioactive ions (UO22+ 1.01 × 10−5–8.32 × 10−5 mol/m2·h, and K+ remains stable at 3.60 × 10−4 mol/m2·h), and the K+/UO22+ separation factors up to 36.2 at an interlayer spacing of 8.8 Å. Using density functional theory and molecular dynamics simulations, we discovered that the effective separation is mainly determined via interlayer spacing and the quantity of introduced functional groups, explaining the anomalous high permeation flux of target ions at low interlayer spacing (4.3 Å). This study deepens our comprehension of interlayer spacing within nanoconfined spaces for ion separation and recovery via graphene membranes, offering valuable insights for the design and synthesis of high-performance nanomembrane materials.

Electrochemical performance of P4Se3 as high-capacity anode materials for monovalent and multivalent ion batteries

The increasing need for advanced anode materials with superior performance in rechargeable batteries has driven investigations into cutting-edge energy storage systems. This study delves into the potential of P4Se3 Molecular Cages (MCs) as innovative anode materials for both monovalent and multivalent ion batteries, including Na ion batteries (NIBs), Mg ion batteries (MIBs), Ca ion batteries (CIBs), Al ion batteries (AIBs), and Zn ion batteries (ZIBs) through a comprehensive Density Functional Theory (DFT) and molecular dynamics (MD) based investigations. The analyses encompass the electronic structure, structural stability, electrochemical performance, charge storage mechanisms, and redox properties to offer valuable insights into the potential of P4Se3 as an anode. The DFT calculations unveil critical aspects of adsorption, diffusion, and reaction kinetics in P4Se3 elucidating its potential as high-capacity and suitable anode material. The exothermic reactions between Na, Mg, Ca, Al, and Zn with host P4Se3 highlight its suitability for the intercalation process in monovalent and multivalent ion batteries. Furthermore, calculated storage capacities for NIB, MIB, CIB, AIB, and ZIB are found as 1484.84 mAhg−1, 519.69 mAhg−1, 1410.60 mAhg−1, 593.93 mAhg−1, and 74.24 mAhg−1 respectively. The voltage profiles indicate favorable open circuit voltages (OCV) of 0.31 V, 0.27 V, 0.55 V, and 3.3 V for NIB, MIB, CIB, and AIB respectively. The study employs climbing image nudged elastic band (Cl-NEB) simulations to compute diffusion barriers faced by monovalent and multivalent ions in the host structure. The calculated minimal diffusion barriers of 0.18 eV for NIB, 0.30 eV for MIB, 0.35 eV for CIB, 0.33 eV for AIB, and 0.71 eV for ZIB indicate fast charging capabilities due to efficient ion movement. Furthermore, the respective calculated values of diffusion coefficient are found as 5.27 × 10−10 m2/s, 5.27 × 10−9, 4.0 × 10−10 m2/s, 5.27 × 10−10 m2/s and 5.27 × 10−11 m2/s and respective values of ionic conductivity σ are found as 4.13 × 10−3 S/m, 14.57 × 10−2 S/m, 30.03 × 10−3 S/m, 16.65 × 10−3 S/m and 0.20 × 10−3 S/m for NIBs, MIBs, CIBs, AIBs and ZIBs. The findings of this study point out suitability of P4Se3 as anode material in monovalent and multivalent ion batteries.

Unveiling aqueous lithium-ion batteries via advanced modelling and characterisation: A review

Aqueous lithium-ion batteries (ALIBs) are promising candidates for sustainable energy storage, offering great advantages in safety, cost, and environmental impact over the conventional nonaqueous LIBs. This paper delves into the forefront of ALIB research in electrolyte formulations, electrode materials, and design strategies of ALIBs that have stemmed from the integration of advanced modelling and characterisation techniques. A detailed examination of multiscale modelling approaches, e.g., density functional theory (DFT), molecular dynamics (MD), microscopic and spectroscopic techniques, e.g., X-ray, Raman, and particularly in situ and in operando methods that provide real-time observations of battery processes, is carried out. We note that the synergy between modelling and characterisation techniques have offered unprecedented insights into the fundamental processes governing ALIB performance, however, more methods that have been demonstrated effective in commercial LIBs, can be employed and contribute to resolving the current bottlenecks of ALIBs. The models at mesoscale, continuum-scale and even larger scales can supplement DFT and MD to investigate the electrochemical processes in electrode-electrolyte interface, bulk electrolyte, porous electrodes, and prototype cells, and cooperate with essential measurements to characterise physicochemical properties of aqueous electrolytes, which are not widely discussed. Other microscopic, structural, and multi-physical characterisations, such as scanning transmission electron microscopy, computed tomography, thermography, and acoustic techniques can provide more insights into lithium intercalation, phase change and degradation, inspiring the theory and model development of ALIBs. By amalgamating the current state-of-the-art and existing challenges, this paper paves the way for future prospects in ALIBs.