In Situ Transmission Electron Microscopy Investigation on Oriented Attachment of Nanodiamonds.

Oriented attachment (OA) plays an important role in the assembly of nanoparticles and the regulation of their size and morphology, which is expected to be an effective means to modulate the properties of nanodiamonds (NDs). However, there remains a dearth of comprehensive investigation into the OA mechanism of NDs. Using in situ transmission electron microscopy, we conducted atomic-resolution investigation on the OA events of ND pairs under electron beam irradiation. The occurrence of an OA event is contingent upon the alignment between two ND surfaces, and the coalesced particles undergo recrystallization to form spherical shapes. Both experimental observations and molecular dynamics (MD) simulations reveal that ND pairs exhibit a preference for coalescing along the {111} surfaces. Additionally, MD simulations indicate that kinetic factors, such as contact surface area and contact angle, also influence the coalescence process.

Effects of pressure on hydrogen diffusion behaviors in MgO.

Hydrogen, as the smallest atom and a key component of water, can penetrate into materials in various forms (e.g., atoms, molecules), which has significant effects on their properties; hence, the diffusion behavior of hydrogen has aroused widespread attention. One of the major compositions in the Earth's interior is MgO. Thus, the diffusion behavior of hydrogen in MgO under high pressure is vital for understanding the water cycle in the Earth's interior. However, the hydrogen diffusion behavior in MgO under high pressure is still poorly understood. Herein, the hydrogen diffusion behaviors in MgO with increasing pressure are systematically investigated in the framework of first-principles methods. Our results show that separated H atoms tend to converge to form H2 molecules, and H2 molecules tend to gather together. The energy barriers of both H and H2 diffusion in MgO increase with pressure. Notably, our results illustrate that hydrogen prefers to diffuse in solid MgO in its molecular state even under high pressure. Furthermore, the attempt frequency of hydrogen in MgO increases with temperature, while it decreases with pressure. This study will deepen our understanding of hydrogen diffusion behavior in MgO under high pressure and provide guidance for studies on particle diffusion in solid materials under extreme conditions.

Influence of defect distribution on the thermoelectric properties of FeNbSb based materials.

Doping and alloying are important methodologies to improve the thermoelectric performance of FeNbSb based materials. To fully understand the influence of point defects on the thermoelectric properties, we have used density functional calculations in combination with the cluster expansion and Monte Carlo methods to examine the defect distribution behaviors in the mesoscopic FeNb1-xVxSb and FeNb1-xTixSb systems. We find that V and Ti exhibit different distribution behaviors in FeNbSb at low temperature: forming the FeNbSb-FeVSb phase separations in the FeNb1-xVxSb system but two thermodynamically stable phases in FeNb1-xTixSb. Based on the calculated effective mass and band degeneracy, it seems the doping concentration of V or Ti in FeNbSb has little effect on the electrical properties, except for one of the theoretically predicted stable Ti phases (Fe6Nb5Ti1Sb6). Thus, an essential methodology to improve the thermoelectric performance of FeNbSb should rely on phonon scattering to decrease the thermal conductivity. According to the theoretically determined phase diagrams of Fe(Nb,V)Sb and Fe(Nb,Ti)Sb, we propose the (composition, temperature) conditions for the experimental synthesis to improve the thermoelectric performance of FeNbSb based materials: lowering the experimental preparation temperature to around the phase boundary to form a mixture of the solid solution and phase separation. The point defects in the solid solution effectively scatter the short-wavelength phonons and the (coherent or incoherent) interfaces introduced by the phase separation can additionally scatter the middle-wavelength phonons to further decrease the thermal conductivity. Moreover, the induced interfaces could enhance the Seebeck coefficient as well, through the energy filtering effect. Our results give insight into the understanding of the impact of the defect distribution on the thermoelectric performance of materials and strengthen the connection between theoretical predictions and experimental measurements.

Recent Advances and Challenges in Ti-Based Oxide Anodes for Superior Potassium Storage.

Developing high-performance anodes is one of the most effective ways to improve the energy storage performances of potassium-ion batteries (PIBs). Among them, Ti-based oxides, including TiO2, K2Ti6O13, K2Ti4O9, K2Ti8O17, Li4Ti5O12, etc., as the intrinsic structural advantages, are of great interest for applications in PIBs. Despite numerous merits of Ti-based oxide anodes, such as fantastic chemical and thermal stability, a rich reserve of raw materials, non-toxic and environmentally friendly properties, etc., their poor electrical conductivity limits the energy storage applications in PIBs, which is the key challenge for these anodes. Although various modification projects are effectively used to improve their energy storage performances, there are still some related issues and problems that need to be addressed and solved. This review provides a comprehensive summary on the latest research progress of Ti-based oxide anodes for the application in PIBs. Besides the major impactful work and various performance improvement strategies, such as structural regulation, carbon modification, element doping, etc., some promising research directions, including effects of electrolytes and binders, MXene-derived TiO2-based anodes and application as a modifier, are outlined in this review. In addition, noteworthy research perspectives and future development challenges for Ti-based oxide anodes in PIBs are also proposed.

Unraveling Atomic-Scale Origins of Selective Ionic Transport Pathways and Sodium-Ion Storage Mechanism in Bi2 S3 Anodes.

It is a major challenge to achieve a high-performance anode for sodium-ion batteries (SIBs) with high specific capacity, high rate capability, and cycling stability. Bismuth sulfide, which features a high theoretical specific capacity, tailorable morphology, and low cost, has been considered as a promising anode for SIBs. Nevertheless, due to a lack of direct atomistic observation, the detailed understanding of fundamental intercalation behavior and Bi2 S3 's (de)sodiation mechanisms remains unclear. Here, by employing in situ high-resolution transmission electron microscopy, consecutive electron diffraction coupled with theoretical calculations, it is not only for the first time identified that Bi2 S3 exhibits specific ionic transport pathways preferred to diffuse along the (110) direction instead of the (200) plane, but also tracks their real-time phase transformations (de)sodiation involving multi-step crystallographic tuning. The finite-element analysis further disclosed multi-reaction induced deformation and the relevant stress evolution originating from the combined effect of the mechanical and electrochemical interaction. These discoveries not only deepen the understanding of fundamental science about the microscopic reaction mechanism of metal chalcogenide anodes but also provide important implications for performance optimization.

Computational Auxiliary for the Progress of Sodium-Ion Solid-State Electrolytes.

All-solid-state sodium batteries (ASSBs) have attracted ever-increasing attention due to their enhanced safety, high energy density, and the abundance of raw materials. One of the remaining key issues for the practical ASSB is the lack of good superionic and electrochemical stable solid-state electrolytes (SEs). Design and manufacturing specific functional materials used as high-performance SEs require an in-depth understanding of the transport mechanisms and electrochemical properties of fast sodium-ion conductors on an atomic level. On account of the continuous progress and development of computing and programming techniques, the advanced computational tools provide a powerful and convenient approach to exploit particular functional materials to achieve that aim. Herein, this review primarily focuses on the advanced computational methods and ion migration mechanisms of SEs. Second, we overview the recent progress on state-of-the-art solid sodium-ion conductors, including Na-ß-alumina, sulfide-type, NASICON-type, and antiperovskite-type sodium-ion SEs. Finally, we outline the current challenges and future opportunities. Particularly, this review highlights the contributions of the computational studies and their complementarity with experiments in accelerating the study progress of high-performance sodium-ion SEs for ASSBs.

Metal-N4@Graphene as Multifunctional Anchoring Materials for Na-S Batteries: First-Principles Study.

Developing highly efficient anchoring materials to suppress sodium polysulfides (NaPSs) shuttling is vital for the practical applications of sodium sulfur (Na-S) batteries. Herein, we systematically investigated pristine graphene and metal-N4@graphene (metal = Fe, Co, and Mn) as host materials for sulfur cathode to adsorb NaPSs via first-principles theory calculations. The computing results reveal that Fe-N4@graphene is a fairly promising anchoring material, in which the formed chemical bonds of Fe-S and N-Na ensure the stable adsorption of NaPSs. Furthermore, the doped transition metal iron could not only dramatically enhance the electronic conductivity and the adsorption strength of soluble NaPSs, but also significantly lower the decomposition energies of Na2S and Na2S2 on the surface of Fe-N4@graphene, which could effectively promote the full discharge of Na-S batteries. Our research provides a deep insight into the mechanism of anchoring and electrocatalytic effect of Fe-N4@graphene in sulfur cathode, which would be beneficial for the development of high-performance Na-S batteries.

Boron-dopant enhanced stability of diamane with tunable band gap.

The structural, electronic, and superconducting properties of B-doped cubic and hexagonal diamane (single layer diamond) were investigated based on the first-principles methods. B atom tends to stay in the substitutional site, and the most stable configuration is the structure with vertical B-B dimer. The formation energy of B-doped diamane is lower than the counterpart of pristine diamane indicating that B dopant can facilitate the synthesis of diamane. The configurations with vertical B-B dimers are semiconductors with tunable band gaps, which decrease with the B concentration increasing due to the interaction between B-B dimers. For example, the band gap of 3.125 mol% and 6.25 mol% B-doped cubic diamane is 1.82 eV and 1.44 eV, respectively. Moreover, configurations with meta-stable B distributions are metals, which have comparable superconducting transition temperatures with B-doped diamond (~4 K).

Superconductivity of boron-doped graphane under high pressure.

Based on first-principles calculations, the properties of B-doped graphane under high pressure up to 380 GPa are investigated. We find that B-doped graphane undergoes a phase transition from phase-α to phase-ß at 6 GPa. Different from pristine graphane (X. Wen, L. Hand, V. Labet, T. Yang, R. Hoffmann, N. W. Ashcroft, A. R. Oganov and A. O. Lyakhov, Graphane sheets and crystals under pressure, Proc. Natl. Acad. Sci. U. S. A., 2011, 108, 6833-6837), phase-γ of B-doped graphane is kinetically unstable. The calculated superconducting transition temperature of B-doped graphane at ambient pressure is 45 K, and pressurization can increase the transition temperature notably, e.g., 77 K at 100 GPa. Both the electronic states at the Fermi level and the electron-phonon coupling are mainly contributed by B-C characteristics, indicating that the B-doping plays a key role in the superconductivity.

Electric-field-controlled superconductor-ferromagnetic insulator transition.

Superconductivity beyond electron-phonon mechanism is always twisted with magnetism. Based on a new field-effect transistor with solid ion conductor as the gate dielectric (SIC-FET), we successfully achieve an electric-field-controlled phase transition between superconductor and ferromagnetic insulator in (Li,Fe)OHFeSe. A dome-shaped superconducting phase with optimal Tc of 43 K is continuously tuned into a ferromagnetic insulating phase, which exhibits an electric-field-controlled quantum critical behavior. The origin of the ferromagnetism is ascribed to the order of the interstitial Fe ions expelled from the (Li,Fe)OH layers by gating-controlled Li injection. These surprising findings offer a unique platform to study the relationship between superconductivity and ferromagnetism in Fe-based superconductors. This work also demonstrates the superior performance of the SIC-FET in regulating physical properties of layered unconventional superconductors.

The polymerization of nitrogen in Li2N2 at high pressures.

The polymerization of nitrogen can be used as high energy density materials. The crystal structures of Li2N2 at high pressures are explored by using the first-principles method combined with evolutionary algorithm. The phase transitions Pmmm → Immm → Pnma → Cmcm-1 → I41/acd are predicted in the pressure range of 0-300 GPa. Enthalpy calculations reveal that the tetragonal phase I41/acd containing the spiral nitrogen chains is stable above 242 GPa, indicating that the polymerization of nitrogen is realized in Li2N2 under pressure.

Effects of vacancy defects on Fe properties incorporated in MgO.

Distributions of Fe in MgO containing Mg vacancy, O vacancy, and Schottky defect are investigated based on the density functional theory (DFT). Our results show that since Mg vacancy will remove electrons from MgO, Fe tends to get close to Mg vacancy but far from O vacancy. The Mg vacancy can decrease the magnetic moment of iron and change its valence state from 2+ to 3+, which leads to ~5% decrease of Fe-O bond length comparable to the effect of 30 GPa external pressure. Furthermore, iron incorporation can increase the Schottky defect concentration of MgO especially in the environment of the Earth's lower mantle, where ~20 mol% Fe-bearing MgO locates at extreme high temperature conditions.

Investigation of iron spin crossover pressure in Fe-bearing MgO using hybrid functional.

Pressure-induced spin crossover behaviors of Fe-bearing MgO were widely investigated by using an LDA + U functional for describing the strongly correlated Fe-O bonding. Moreover, the simulated spin crossover pressures depend on the applied U values, which are sensitive to environments and parameters. In this work, the spin crossover pressures of (Mg1-x ,Fe x )O are investigated by using the hybrid functional with a uniform parameter. Our results indicate that the spin crossover pressures increase with increasing iron concentration. For example, the spin crossover pressure of (Mg0.03125,Fe0.96875)O and FeO was 56 GPa and 127 GPa, respectively. The calculated crossover pressures agreed well with the experimental observations. Therefore, the hybrid functional should be an effective method for describing the pressure-induced spin crossover behaviors in transition metal oxides.

Opposite pressure effects in the orbitally-induced Peierls phase transition systems CuIr2S4 and MgTi2O4.

The iso-spinel structural systems CuIr2S4 and MgTi2O4 exhibit phase transitions of a similar nature at ∼230 K and ∼260 K respectively, which are explained as an orbitally-induced Peierls phase transition. However, in this work, we uncover that the applied pressure has opposite pressure effects on the phase transitions in CuIr2S4 and MgTi2O4. As the pressure increases, the phase transition temperature (TMI) for CuIr2S4 increases while that for MgTi2O4 decreases. In addition, the phase transition intensity becomes weaker for CuIr2S4 but gets stronger for MgTi2O4 under pressure. Our results indicate that the applied pressure suppresses the metallic phase in CuIr2S4, while enhances that in MgTi2O4. Combining the experimental observations with first-principles electronic structure calculations, we suggest that the opposite pressure effects in CuIr2S4 and MgTi2O4 originate from the different orbital ordering configurations (dxy, dyz/dxz) caused by different lattice distortions in these two systems. Our findings indicate directly that the interplay between the orbital and lattice degrees of freedom plays an important role in the orbitally-induced Peierls phase transition.