Tunable abundant valley Hall effect and chiral spin-valley locking in Janus monolayer VCGeN4.

It is both conceptually and practically fascinating to explore fundamental research studies and practical applications of two-dimensional systems with the tunable abundant valley Hall effect. In this work, based on first-principles calculations, the tunable abundant valley Hall effect is proved to appear in Janus monolayer VCGeN4. When the magnetization is along the out-of-plane direction, VCGeN4 is an intrinsic ferromagnetic semiconductor with a valley feature. The intriguing spontaneous valley polarization exists in VCGeN4 due to the common influence of broken inversion and time-reversal symmetries, which makes it easier to realize the anomalous valley Hall effect. Furthermore, we observe that the valley-non-equilibrium quantum anomalous Hall effect is driven by external strain, which is located between two half-valley-metal states. When reversing the magnetization, the spin flipping makes the position of the edge state to change from one valley to another valley, demonstrating an intriguing behavior known as chiral spin-valley locking. Although the easy magnetic axis orientation is along the in-plane direction, we can utilize an external magnetic field to transform the magnetic axis orientation. Moreover, it is found that the valley state, electronic and magnetic properties can be well regulated by the electric field. Our works explore the mechanism of the tunable abundant valley Hall effect by applying an external strain and electric field, which provides a perfect platform to investigate the spin, valley, and topology.

Novel valley character and tunable quasi-half-valley metal state in Janus monolayer VSiGeP4.

The manipulation and regulation of valley characteristics have aroused widespread interest in emerging information fields and fundamental research. Realizing valley polarization is one crucial issue for spintronic and valleytronic applications, the concepts of a half-valley metal (HVM) and ferrovalley (FV) materials have been put forward. Then, to separate electron and hole carriers, a fresh concept of a quasi-HVM (QHVM) has been proposed, in which only one type of carrier is valley polarized for electron and hole carriers. Based on first-principles calculations, we demonstrate that the Janus monolayer VSiGeP4 has QHVM character. To well regulate the QHVM state, strain engineering is utilized to adjust the electronic and valley traits of monolayer VSiGeP4. In the discussed strain range, monolayer VSiGeP4 always favors the ferromagnetic ground state and out-of-plane magnetization, which ensures the appearance of spontaneous valley polarization. It is found that the QHVM state can be induced in different electronic correlations (U), and the strain can effectively tune the valley, magnetic, and electronic features to maintain the QHVM state under various U values. Our work opens up a new research idea in the design of multifunctional spintronic and valleytronic devices.

Quantum anomalous Hall effect with a high and tunable Chern number in monolayer NdN2.

Due to the presence of dissipationless edge states, the quantum anomalous Hall (QAH) insulator has garnered significant attention for both fundamental research and practical application. However, the majority of QAH insulators suffer from a low Chern number (C = 1), and the Chern number is basically unadjustable, which constrains their potential application in spintronic devices. Here, based on a tight-binding model and first-principles calculations, we propose that two-dimensional (2D) ferromagnetic monolayer NdN2 exhibits a high-Chern-number QAH effect with C = ±3, accompanied by a nontrivial band gap of 97.4 meV. More importantly, by manipulating the magnetization orientation in the xz plane, the Chern number of 2D NdN2 can be further tuned between C = ±3 and C = ±1. When the magnetization vector is confined to the xy plane, the monolayer NdN2 would exhibit either a Dirac half-semimetal or in-plane QAH phase. Moreover, the QAH effect with a higher Chern number C = 9 can be achieved by constructing a multilayer van der Waals heterostructure composed of monolayers NdN2 and BN with alternative stacking order. These findings provide a reliable platform for exploring the novel QAH effect and developing high-performance topological devices.

High-Performance Li-S Batteries with a Minimum Shuttle Effect: Disproportionation of Dissolved Polysulfide to Elemental Sulfur Catalyzed by a Bifunctional Carbon Host.

A long cycle-life Li-S battery (both the coin cell and pouch cell) is reported with minimum shuttle effect. The performance was achieved with a bifunctional carbon material with three unique features. The carbon can catalyze the disproportionation of dissolved long-chain polysulfide ions to elemental sulfur; the carbon can ensure homogeneous precipitation of Li sulfide on the host carbon, and the carbon has a honeycomb porous structure, which can store sulfur better. All the features are demonstrated experimentally and reported in this paper. Few dissolved polysulfides are found by high-performance liquid chromatography in the electrolyte of the Li-S batteries during cycling, and only dissolved elemental sulfur is detected. The unique porous structure of the carbon made from raw silk is revealed by scanning electron microscopy. The N-containing functionalities that were introduced to carbon from the amino acids of raw silk can catalyze the disproportionation of the dissolved Sn2- to solid S8 at the cathode side, thereby mitigating the shuttle effect. In addition, the hierarchical honeycomb porous structures generated by a carbonization process can physically trap high-order lithium polysulfides and sustain the volume change of sulfur. With the synergistic effects of the unique structures and characteristics of the carbon prepared at 800 °C, the sulfur/carbon composite delivers a high reversible capacity of over 1000 mAh g-1 after 100 cycles with a sulfur content of 1.2 mg cm-2 in a pouch cell.

Electronic-correlation induced sign-reversible Berry phase and quantum anomalous valley Hall effects in Janus monolayer OsClBr.

Topological phase transition can be induced by electronic correlation effects combined with spin-orbit coupling (SOC). Here, based on the first-principles calculations +U approach, the influence of electronic correlation effects and SOC on topological and electronic properties of the Janus monolayer OsClBr is investigated. With intrinsic out-of-plane (OOP) magnetic anisotropy, the Janus monolayer OsClBr exhibits a sequence of states, namely, the ferrovalley (FV) to half-valley-metal (HVM) to quantum anomalous valley Hall effect (QAVHE) to HVM to FV states with increasing U values. The QAVHE is characterized by a chiral edge state linking the conduction and valence bands with a Chern number C = 1, which is closely associated with the band inversion between dx2-y2/dxy and dz2 orbitals, and sign-reversible Berry curvature. The section with larger U values (2.31-2.35 eV) is very essential for determining the new HVM and QAVHE states, and also proves that a strong electron correlation effect exists in the interior of the Janus monolayer OsClBr. When taking into consideration a representative U value (U = 2.5 eV), a valley polarization value of 157 meV can be observed, which can be switched by reversing the magnetization direction of Os atoms. It is noteworthy that the Curie temperature (TC) strongly depends on the electronic correlation effects. Our work provides a comprehensive discussion on the electronic and topological properties of the Janus monolayer OsClBr, and demonstrates that the electronic correlation effects combined with SOC can drive the emergence of QAVHE, which will open up new opportunities for valleytronic, spintronic, and topological nanoelectronic applications.

Spontaneous valley polarization and valley-nonequilibrium quantum anomalous Hall effect in Janus monolayer ScBrI.

Topology and ferrovalley (FV) are two essential concepts in emerging device applications and the fundamental research field. To date, relevant reports are extremely rare about the coupling of FV and topology in a single system. By Monte Carlo (MC) simulations and first-principles calculations, a stable intrinsic FV ScBrI semiconductor with high Curie temperature (TC) is predicted. Because of the combination of spin-orbital coupling (SOC) and exchange interaction, the Janus monolayer ScBrI shows a spontaneous valley polarization of 90 meV, which is located in the top valence band. For the magnetization direction perpendicular to the plane, the changes from FV to half-valley-metal (HVM), to valley-nonequilibrium quantum anomalous Hall effect (VQAHE), to HVM, and to FV can be induced by strain engineering. It is worth noting that there are no particular valley polarization and VQAHE states for in-plane (IP) magnetic anisotropy. By obtaining the real magnetic anisotropy energy (MAE) under different strains, due to spontaneous valley polarization, intrinsic out-of-plane (OOP) magnetic anisotropy, a chiral edge state, and a unit Chern number, the VQAHE can reliably appear between two HVM states. The increasing strains can induce VQAHE, which can be clarified by a band inversion between dx2-y2/dxy and dz2 orbitals, and a sign-reversible Berry curvature. Once synthesized, the Janus monolayer ScBrI would find more significant applications in topological electronic, valleytronic, and spintronic nanodevices.

Strain-tunable skyrmions in two-dimensional monolayer Janus magnets.

The Dzyaloshinskii-Moriya interaction (DMI), which only exists in noncentrosymmetric systems, plays an important role in the formation of exotic chiral magnetic states. However, the absence of the DMI occurs in most two-dimensional (2D) magnetic materials due to their intrinsic inversion symmetry. Here, by using first-principles calculations, we demonstrate that a significant DMI can be obtained in a series of Janus monolayers of dichalcogenides XSeTe (X = Nb, Re) in which the difference between Se and Te on the opposite sides of X breaks the inversion symmetry. Remarkably, the DMI amplitudes of NbSeTe (1.78 meV) and ReSeTe (4.82 meV) are larger than the experimental value of Co/graphene (0.16 meV), and NbSeTe and ReSeTe monolayers have a high Curie temperature of 1023 K and 689 K, respectively. Through the micromagnetic simulation of XSeTe (X= Nb, Re) simulations, we also find that the ReSeTe monolayer can performance for skyrmion states by applying an external magnetic field, and importantly, the skyrmion states can be regulated and controlled under external strain. The findings pave the way for device concepts using chiral magnetic structures in specially designed 2D ferromagnetic materials.

Enhanced OER Performance and Dynamic Transition of Surface Reconstruction in LaNiO3 Thin Films with Nanoparticles Decoration.

In an electrocatalytic process, the cognition of the active phase in a catalyst has been regarded as one of the most vital issues, which not only boosts the fundamental understanding of the reaction procedure but also guides the engineering and design for further promising catalysts. Here, based on the oxygen evolution reaction (OER), the stepwise evolution of the dominant active phase is demonstrated in the LaNiO3 (LNO) catalyst once the single-crystal thin film is decorated by LNO nanoparticles. It is found that the OER performance can be dramatically improved by this decoration, and the catalytic current density at 1.65 V can be enhanced by ≈1000% via ≈109 cm-2 nanoparticle adhesion after extracting the contribution of surface enlargement. Most importantly, a transition of the active phase from LNO to NiOOH via surface reconstruction with the density of LNO nanoparticles is demonstrated. Several mechanisms in terms of this active phase transition are discussed involving lattice orientation-induced change of the surface energy profile, the lattice oxygen participation, and the A/B-site ions leaching during OER cycles. This study suggests that the active phases in transition metal-based OER catalysts can transform with morphology, which should be corresponding to distinct engineering strategies.

Two -dimensional semimetal AlSb monolayer with multiple nodal-loops and extraordinary transport properties under uniaxial strain.

Two-dimensional (2D) nodal-loop semimetal (NLSM) materials have attracted much attention for their high-speed and low-consumption transporting properties as well as their fantastic symmetry protection mechanisms. In this paper, using systematic first-principles calculations, we present an excellent NLSM candidate, a 2D AlSb monolayer, in which the conduction and valence bands cross with each other forming fascinating multiple nodal-loop (NL) states. The NLSM properties of the AlSb monolayer are protected by its glide mirror symmetry, which was confirmed using a symmetry-constrained six-band tight-binding model. The transport properties of the AlSb monolayer under in-plane uniaxial strains are also studied, based on a non-equilibrium Green's function method. It is found that both compressive and tensile strains from -10% to 10% improve the transporting properties of AlSb, and it is interesting to see that flexure configurations are energetically favored when compressive uniaxial strains are applied. Our studies not only provide a novel 2D NLSM candidate with a new symmetry protection mechanism, but also raise the novel possibility for the detection of out-of-plane flexure in 2D semimetal materials.

High excellent hydrogen evolution characteristics and novel mechanism of two-dimensional tetra-phase OsN2 and ReN2.

It is essential to find a kind of electrocatalyst for hydrogen evolution reduction (HER) comparable with a noble metal that has good conductivity and abundant active sites. Based on systematic searches by first-principles calculations, we discovered two-dimensional transition-metal nitrides, tetra-phase OsN2 and ReN2 monolayers, as potential HER electrocatalysts with superior thermodynamic and kinetic stability. They exhibited excellent catalytic activity due to the presence of multiple active sites with a density of 8 × 1015 site per cm2 and an overpotential close to 0. In addition, we also found that the synergistic effect of strain and coverage makes them have a good hydrogen evolution activity. The ΔGH of the OsN2 monolayer at 1% tensile strain under 3/4 hydrogen coverage is 0.02 eV, and that of ReN2 at 1/2 hydrogen coverage could decrease to 0.001 eV. Different from other common transition metal nitrides, we found that the active sites of OsN2 and ReN2 monolayers are both at nitrogen atoms, which could be further understood by the crystal orbital Hamiltonian population analysis between N and metal atoms. All these interesting findings not only provide new excellent candidates but also provide new insights into the mechanism of hydrogen evolution of nitrides.

Prediction of the ferrovalley property with sizable valley splitting in Janus monolayer GdBrI.

The exploitation of two-dimensional (2D) ferrovalley materials is of great significance in promoting the development of novel information storage devices, which is garnering increasing interest nowadays. However, the currently discovered 2D ferrovalley materials are very limited, and some of them still suffer from the drawback of small valley splitting, which seriously hinders their application in valleytronics. Herein, using first-principles calculations, we predict a promising 2D ferrovalley material, Janus monolayer GdBrI, which harbors sizable valley splitting and the anomalous valley Hall effect (AVHE). Monolayer GdBrI is a stable ferromagnetic semiconductor with an easy magnetization plane and magnetic transition temperature of 264.5 K. When the magnetization orientation is toward the z direction, valley polarization with a large splitting of 120.4 meV is achieved in the valence band due to the synergetic effect between the magnetic exchange interaction and spin-orbit coupling. The valley-contrasting Berry curvature gives rise to the AVHE in the monolayer. The magnitude of valley splitting can be continuously tuned by varying the magnetization orientation, biaxial strain and perpendicular electric field. These findings offer Janus monolayer GdBrI as a potential candidate for spintronic and valleytronic applications.

Possibility of regulating valley-contrasting physics and topological properties by ferroelectricity in functionalized arsenene.

A two-dimensional (2D) multifunctional material, which couples multiple physical properties together, is both fundamentally intriguing and practically appealing. Here, based on first-principles calculations and tight-binding (TB) model analysis, the possibility of regulating the valley-contrasting physics and nontrivial topological properties via ferroelectricity is investigated in monolayer AsCH2OH. Reversible electric polarization is accessible via the rotation operation on the ligand. The broken inversion symmetry and the spin-orbit coupling (SOC) would lead to valley spin splitting, spin-valley coupling and valley-contrasting Berry curvature. More importantly, the reversal of electric polarization can realize the nonvolatile control of valley-dependent properties. Besides, the nontrivial topological state is confirmed in the monolayer AsCH2OH, which is robust against the rotation operation on the ligand. The magnitude of polarization, valley spin splitting and bulk band gap can be effectively modulated by the biaxial strain. The H-terminated SiC is demonstrated to be an appropriate candidate for encapsulating monolayer AsCH2OH, without affecting its exotic properties. These findings provide insights into the fundamental physics for the coupling of the valley-contrasting phenomenon, topological properties and ferroelectricity, and open avenues for exploiting innovative device applications.

Magnetic anisotropy and ferroelectric-driven magnetic phase transition in monolayer Cr2Ge2Te6.

Monolayer Cr2Ge2Te6 (ML-CGT) has attracted broad interest due to its novel electronic and magnetic properties. However, there are still controversies on the origin of its intrinsic magnetism. Here, by exploring the electronic and magnetic properties of ML-CGT, we find that the magnetic shape anisotropy (MSA) is vital for establishing the long-range ferromagnetism, except for the contribution from magnetocrystalline anisotropy energy (MCA). Electronic band analysis, combined with atomic- and orbital-resolved magnetic anisotropy from a second-order perturbation theory, further reveals that the MCA of ML-CGT is mainly originated from hybridized Te-py and -pz orbitals. The MSA from magnetic Cr atoms in ML-CGT is larger than MCA, resulting in an in-plane magnetic anisotropy. Noticeably, by constructing a heterostructure (HTS) with ferroelectric Sc2CO2, CGT undergoes an in-plane to out-of-plane spin reorientation via ferroelectric polarization switching, accompanied with an electronic property transition from semiconductor to half-metal. The Curie temperature of CGT/Sc2CO2 HTS can be enhanced to 92.4 K under the ferroelectric polarization, which is much higher than that of pristine ML-CGT (34.7 K). These results not only clarify the contradiction of magnetic mechanism of ML-CGT in previous experimental and theoretical works, but also open the door for realizing nonvolatile magnetic memory devices based on a multifunctional ferromagnetic/ferroelectric HTS.

Anisotropic nodal loop in NiB2 monolayer with nonsymmorphic configuration.

Two-dimensional (2D) materials featuring a nodal-loop (NL) state have been drawing considerable attention in condensed matter physics and materials science. Owing to their structural polymorphism, recent high-profile metal-boride films have great advantages and the potential to realize a NL. Herein, a 2D NiB2 monolayer with an anisotropic NL nature is proposed and investigated using first-principles calculations. We show that the NiB2 monolayer has excellent thermal dynamics stability, suggesting the possibility of its synthesis in experiments. Remarkably, the NL with a considerable Fermi velocity is demonstrated to be protected by nonsymmorphic glide mirror symmetry, instead of the widely known horizontal mirror symmetry. Accompanied by the proper preservation of the NL, strain engineering can not only regulate the anisotropy of the NL but also give rise to a self-doping phenomenon characterized by effective modulation of the carrier type and concentration. Moreover, this NL state is robust against the correlation effect. These findings pave the way for exploring nonsymmorphic-symmetry-enabled NL nature in 2D metal-borides.

Impedance investigation of the high temperature performance of the solid-electrolyte-interface of a wide temperature electrolyte.

The high temperature cycling performance of a wide temperature electrolyte and the solid electrolyte interphase (SEI) along the cycling were investigated using a three-electrode pouch cell. The electrolyte developed in our lab demonstrated outstanding low temperature performance. The electrolyte was found to have a good and stable cycling performance at a high temperature in comparison with a state-of-the-art baseline electrolyte. Electrochemical impedance spectroscopy (EIS) was conducted on the anode, the cathode and the full cell independently with a reference embedded pouch cell. The distribution of relaxation times (DRT) transformation was calculated from the EIS spectrum. An equivalent circuit model was used to fit the anode EIS data and the electrochemical process on the anode was revealed. We concluded that a denser SEI layer was built on the anode of the improved electrolyte.

Electrode Architecture Design to Promote Charge-Transport Kinetics in High-Loading and High-Energy Lithium-Based Batteries.

Rechargeable lithium-ion batteries have built much of our modern society. Developing high-loading and high-energy batteries have become an inevitable trend to satisfy the ever-growing demand of energy consumption. However, issues related to mechanical instability and electrochemical polarization have become more prominent accompanying the increase of electrode thickness. How to establish a robust and rapid charge transport network within the electrode architecture plays a vital role for the mechanical property and the reaction dynamics of thick electrodes. In this review, principles of charge transport mechanism and challenges of thick electrode development are elaborated. Next, recent progress on advanced electrode architecture design focused on structural engineering is summarized. Finally, a transmission line model is proposed as an effective tool to guide the engineering of thick electrodes.

Janus PtXO (X = S, Se) monolayers: the visible light driven water splitting photocatalysts with high carrier mobilities.

Triggered by the recent experimental synthesis of the Janus PtSSe monolayer, we use the first-principles calculations to predict two new Janus photocatalysts PtXO (X = S, Se), based on the systematic investigations of the structural stabilities, electronic structures, band alignments, catalytic activity and optical absorption. The two Janus structures are found to be mechanically, dynamically and thermodynamically stable, and have suitable band edge positions for the overall water splitting. Owing to the high electron mobility (up to 2164.95 cm2 V-1 s-1) and large disparity between the electron and hole mobilities, together with the indirect band gaps and the intrinsic dipole induced built-in electric fields, the photogenerated electrons/holes can be efficiently separated in PtXO. Moreover, the S/Se vacancy can effectively lower the free energy difference of the HER, making the catalytic reactions occur spontaneously under the potentials of photoexcited electrons and holes. Large optical absorption coefficients (105 cm-1) are also confirmed in the visible light range, and the biaxial tensile strain can further enhance the optical absorption while maintaining the capability of the overall water splitting. Our results not only propose two new Janus materials by demonstrating the possibility of experimental realization, but also indicate that PtXO are peculiar candidates for photocatalytic water splitting.

Two-dimensional Weyl semi-half-metallic NiCS3 with a band structure controllable by the direction of magnetization.

Two-dimensional (2D) Weyl semi-half-metals (WSHMs) have attracted tremendous interest for their fascinating properties combining half-metallic ferromagnetism and Weyl fermions. In this work, we present a NiCS3 monolayer as a new 2D WSHM material using systematic first-principles calculations. It has 12 fully spin-polarized Weyl nodal points in one spin channel with a Fermi velocity of 3.18 × 105 m s-1 and a fully gapped band structure in the other spin channel. It exhibits good mechanical and thermodynamic stabilities and the Curie temperature is estimated to be 403 K. The Weyl points are protected by vertical mirror plane symmetry along Γ-K, and each of them remains gapless even under spin-orbit coupling when the direction of spin is perpendicular to the Γ-K line including the Weyl point, which makes it possible to control the opening and closing of Weyl points by applying and rotating external magnetic fields. Our work not only provides a promising 2D WSHM material to explore the fundamental physics of symmetry protected ferromagnetic Weyl fermions, but also reveals a potential mechanism of band engineering of 2D WSHM materials in spintronics.

A novel spin-valley-coupled nodal-ring semimetal in single-layer Ta2C3.

Nodal-ring semimetals with band crossing are the new type of quantum materials that have attracted considerable interest from scholars for research. In general, the spin-orbit coupling (SOC) effect opens a band gap at the Dirac point. Therefore, finding 2D nodal-ring semimetals with resistance to SOC has more challenges. Based on first-principles calculations, we propose here that the two-dimensional (2D) Ta2C3 monolayer is a novel nodal-ring semimetal. In particular, Ta2C3 forms six closed rings in the Brillouin zone (BZ) with SOC, which originates from the dxy,x2-y2 orbitals of Ta and the pz orbitals of C. The nodal-ring bands at the K point in Ta2C3 exhibits characteristics of valley splitting and spin polarization due to the breaking of inversion symmetry and SOC. The masximal spin-splitting at the K point is as large as 268.87 meV and 61.90 meV for the conduction band minimum (CBM) and valence band maximum (VBM), respectively. The massless Dirac fermions in the non-equivalent valley have the opposite Berry curvature and spin moment. Therefore, 2D Ta2C3 is novel spin-valley-coupled nodal-ring semimetal. In addition, we found interesting negative differential resistance effects when calculating its transport properties. Our results not only provide an ideal platform for studying the combination of new physical properties, spintronics and valleytronics, but also open the way for designing low-power and fast-transport electronic devices.

Half-Dirac semimetals and the quantum anomalous Hall effect in Kagome Cd2N3 lattices.

Half-Dirac semimetals (HDSs), which possess 100% spin-polarizations for Dirac materials, are highly desirable for exploring various topological phases of matter as low-dimensionality opens unprecedented opportunities for manipulating the quantum state of low-cost electronic nanodevices. The search for high-temperature HDSs is still a current hotspot and yet challenging experimentally. Herein based on first-principles calculations, we propose the realization of Half Dirac semimetals (HDS) in two-dimensional (2D) Kagome transition-metal nitride Cd2N3, which is robust against strain engineering. Monte Carlo simulations reveal that Cd2N3 possesses a Curie temperature reaching up to T C = 225 K, which is much higher than that of the reported monolayers CrI3 (T C = 45 K) and Cr2Ge2Te6 (T C = 20 K). The band crossings in Cd2N3 are gapped out by the spin-orbit coupling, which brings about the quantum anomalous Hall (QAH) effect with a sizeable band gap of E g = 4.9 meV, characterized by the nonzero Chern number (C = 1) and chiral edge states. A tight-binding model is further used to clarify the origin of HDSs and nontrivial electronic properties. The results suggest monolayer transition-metal nitrides as a promising platform to explore fascinating physical phenomena associated with novel 2D emergent HDSs and QAH insulators toward realistic spintronics devices, thus stimulating experimental interest.