Magnetically Enhanced Oxygen Evolution Reaction in Mild Alkaline Electrolytes by Building Catalysts on Magnetic Frame.

Under large current densities, the excessive hydroxide ion (OH) consumption hampers alkaline water splitting involving the oxygen evolution reaction (OER). High OH concentration (≈30 wt.%) is often used to enhance the catalytic activity of OER, but it also leads to higher corrosion in practical systems. To achieve higher catalytic activity in low OH concentration, catalysts on magnetic frame (CMF) are built to utilize the local magnetic convection induced from the host frame's magnetic field distributions. This way, a higher reaction rate can be achieved in relatively lower OH concentrations. A CMF model system with catalytically active CoFeOx nanograins grown on the magnetic Ni foam is demonstrated. The OER current of CoFeOx@NF receives ≈90% enhancement under 400 mT (900 mA cm-2 at 1.65 V) compared to that in zero field, and exhibits remarkable durability over 120 h. As a demonstration, the water-splitting performance sees a maximum 45% magnetic enhancement under 400 mT in 1 m KOH (700 mA cm-2 at 2.4 V), equivalent to the concentration enhancement of the same electrode in a more corrosive 2 m KOH electrolyte. Therefore, the catalyst-on-magnetic-frame strategy can make efficient use of the catalysts and achieve higher catalytic activity in low OH concentration by harvesting local magnetic convection.

Extra storage capacity in transition metal oxide lithium-ion batteries revealed by in situ magnetometry.

In lithium-ion batteries (LIBs), many promising electrodes that are based on transition metal oxides exhibit anomalously high storage capacities beyond their theoretical values. Although this phenomenon has been widely reported, the underlying physicochemical mechanism in such materials remains elusive and is still a matter of debate. In this work, we use in situ magnetometry to demonstrate the existence of strong surface capacitance on metal nanoparticles, and to show that a large number of spin-polarized electrons can be stored in the already-reduced metallic nanoparticles (that are formed during discharge at low potentials in transition metal oxide LIBs), which is consistent with a space charge mechanism. Through quantification of the surface capacitance by the variation in magnetism, we further show that this charge capacity of the surface is the dominant source of the extra capacity in the Fe3O4/Li model system, and that it also exists in CoO, NiO, FeF2 and Fe2N systems. The space charge mechanism revealed by in situ magnetometry can therefore be generalized to a broad range of transition metal compounds for which a large electron density of states is accessible, and provides pivotal guidance for creating advanced energy storage systems.

Evolution of interlayer and intralayer magnetism in three atomically thin chromium trihalides.

We conduct a comprehensive study of three different magnetic semiconductors, CrI3, CrBr3, and CrCl3, by incorporating both few-layer and bilayer samples in van der Waals tunnel junctions. We find that the interlayer magnetic ordering, exchange gap, magnetic anisotropy, and magnon excitations evolve systematically with changing halogen atom. By fitting to a spin wave theory that accounts for nearest-neighbor exchange interactions, we are able to further determine a simple spin Hamiltonian describing all three systems. These results extend the 2D magnetism platform to Ising, Heisenberg, and XY spin classes in a single material family. Using magneto-optical measurements, we additionally demonstrate that ferromagnetism can be stabilized down to monolayer in more isotropic CrBr3, with transition temperature still close to that of the bulk.

Reacquainting the Electrochemical Conversion Mechanism of FeS2 Sodium-Ion Batteries by Operando Magnetometry.

In spite of the excellent electrochemical performance in lithium-ion batteries (LIBs), transition-metal compounds usually show inferior capacity and cyclability in sodium-ion batteries (SIBs), implying different reaction schemes between these two types of systems. Herein, coupling operando magnetometry with electrochemical measurement, we peformed a comprehensive investigation on the intrinsic relationship between the ion-embedding mechanisms and the electrochemical properties of the typical FeS2/Na (Li) cells. Operando magnetometry together with ex-situ transmission electron microscopy (TEM) measurement reveal that only part of FeS2 is involved in the conversion reaction process, while the unreactive parts form "inactive cores" that lead to the low capacity. Through quantification with Langevin fitting, we further show that the size of the iron grains produced by the conversion reaction are much smaller in SIBs than that in LIBs, which may lead to more serious pulverization, thereby resulting in worse cycle performance. The underlying reason for the above two above phenomena in SIBs is the sluggish kinetics caused by the larger Na-ion radius. Our work paves a new way for the investigation of novel SIB materials with high capacity and long durability.

Reference-frame-independent measurement-device-independent quantum key distribution with mismatched-basis statistics.

The source flaw associated with the basis vector in the reference-frame-independent measurement-device-independent quantum key distribution (RFI-MDI-QKD) has not been systematically studied. As a result, it is often assumed that bit error is equal to phase error, which is not theoretically rigorous. Here, we propose a postprocessing method to estimate the phase error rate from the discarded mismatched-basis statistics, where the qubit source does not need to be characterized in detail. The source flaw in the basis vector of the RFI-MDI-QKD protocol can thus be corrected using this method. The numerical simulation results clearly demonstrate that the RFI-MDI-QKD protocol with uncharacterized sources is also insensitive to the misalignment of the reference frame.

Tailored Tunnel Magnetoresistance Response in Three Ultrathin Chromium Trihalides.

Materials that demonstrate large magnetoresistance have attracted significant interest for many decades. Extremely large tunnel magnetoresistance (TMR) has been reported by several groups across ultrathin CrI3 by exploiting the weak antiferromagnetic coupling between adjacent layers. Here, we report a comparative study of TMR in all three chromium trihalides (CrX3, X = Cl, Br, or I) in the two-dimensional limit. As the materials exhibit different transition temperatures and interlayer magnetic ordering in the ground state, tunneling measurements allow for an easy determination of the field-temperature phase diagram for the three systems. By changing sample thickness and biasing conditions, we then demonstrate how to maximize and further tailor the TMR response at different temperatures for each material. In particular, near the magnetic transition temperature, TMR is nonsaturating up to the highest fields measured for all three compounds owing to the large, field-induced exchange coupling.

Spin manipulation with magnetic semiconductor barriers.

Magnetic semiconductors are a class of materials with special spin-filtering capabilities with magnetically tunable energy gaps. Many of these materials also possess another intrinsic property: indirect exchange interaction between the localized magnetic moments and the adjacent free electrons, which manifests as an extremely large effective magnetic field applying only on the spin degrees of freedom of the free electrons. Novel device concepts can be created by taking advantage of these properties. We discuss in the article the basic principles of these phenomena, and potential ways of applying them in constructing spintronic devices.

Volatile and Nonvolatile Programmable Iontronic Memristor with Lithium Imbued TiOx for Neuromorphic Computing Applications.

We demonstrate a lithium (Li) imbued TiOx iontronic device that exhibits synapse-like short-term plasticity behavior without requiring a forming process beforehand or a compliance current during switching. A solid-state electrolyte lithium phosphorus oxynitride (LiPON) behaves as the ion source, and the embedding and releasing of Li ions inside the cathodic like TiOx renders volatile conductance responses from the device and offers a natural platform for hardware simulating neuron functionalities. Besides, these devices possess high uniformity and great endurance as no conductive filaments are present. Different short-term pulse-based phenomena, including paired pulse facilitation, post-tetanic potentiation, and spike rate-dependent plasticity, were observed with self-relaxation characteristics. Based on the voltage excitation period, the time scale of the volatile memory can be tuned. Temperature measurement reveals the ion displacement-induced conductance channels become frozen below 220 K. In addition, the volatile analog devices can be configured into nonvolatile memory units with multibit storage capabilities after an electroforming process. Therefore, on the same platform, we can configure volatile units as nonlinear dynamic reservoirs for performing neuromorphic training and the nonvolatile units as the weight storage layer. We proceed to use voice recognition as an example with the tunable time constant relationship and obtain 94.4% accuracy with a minimal training data set. Thus, this iontronic platform can effectively process and update temporal information for reservoir and neuromorphic computing paradigms.

Magnetic Field Enhanced Oxygen Reduction Reaction via Oxygen Diffusion Speedup.

The mass-transfer of oxygen in liquid phases (including in the bulk electrolyte and near the electrode surface) is a critical step to deliver oxygen to catalyst sites (especially immersed catalyst sites) and use the full capacity of oxygen reduction reaction (ORR). Despite the extensive efforts of optimizing the complex three-phase reaction interfaces to enhance the gaseous oxygen transfer, strong limitations remain due to oxygen's poor solubility and slow diffusion in electrolytes. Herein, a magnetic method for boosting the directional hydrodynamic pumping of oxygen toward immersed catalyst sites is demonstrated which allows the ORR to reach otherwise inaccessible catalytic regions where high currents normally would have depleted oxygen. For Pt foil electrodes without forced oxygen saturation in KOH electrolytes, the mass-transfer-limited current densities can be improved by 60% under an external magnetic field of 435 mT due to the synergistic effect between bulk- and surface-magnetohydrodynamic (MHD) flows induced by Lorentz forces. The residual magnetic fields are further used at the surface of magnetic materials (such as CoPt alloys and Pt/FeCo heterostructures) to enhance the surface-MHD effect, which helps to retain part of the ORR enhancement permanently without applying external magnetic fields.

Space-Charge Control of Magnetism in Ferromagnetic Metals: Coupling Giant Magnitude and Robust Endurance.

Ferromagnetic metals show great prospects in ultralow-power-consumption spintronic devices, due to their high Curie temperature and robust magnetization. However, there is still a lack of reliable solutions for giant and reversible voltage control of magnetism in ferromagnetic metal films. Here, a novel space-charge approach is proposed which allows for achieving a modulation of 30.3 emu/g under 1.3 V in Co/TiO2 multilayer granular films. The robust endurance with more than 5000 cycles is demonstrated. Similar phenomena exist in Ni/TiO2 and Fe/TiO2 multilayer granular films, which shows its universality. The magnetic change of 107% in Ni/TiO2 underlines its potential in a voltage-driven ON-OFF magnetism. Such giant and reversible voltage control of magnetism can be ascribed to space-charge effect at the ferromagnetic metals/TiO2 interfaces, in which spin-polarized electrons are injected into the ferromagnetic metal layer with the adsorption of lithium-ions on the TiO2 surface. These results open the door for a promising method to modulate the magnetization in ferromagnetic metals, paving the way toward the development of ionic-magnetic-electric coupled applications.

Revealing interfacial space charge storage of Li+/Na+/K+ by operando magnetometry.

Interfacial space charge storage between ionic and electronic conductor is a promising scheme to further improve energy and power density of alkali metal ion batteries (AMIBs). However, the general behavior of space charge storage in AMIBs has been less investigated experimentally, mostly due to the complicated electrochemical behavior and lack of proper characterization techniques. Here, we use operando magnetometry to verify that in FeSe2 AMIBs, abundant Li+/Na+/K+ (M+) can be stored at M2Se phase while electrons accumulate at Fe nanoparticles, forming interfacial space charge layers. Magnetic and dynamics tests further demonstrate that with increasing ionic radius from Li+, Na+ to K+, the reaction kinetics can be hindered, resulting in limited Fe formation and reduced space charge storage capacity. This work lays solid foundation for studying the complex interfacial effect in electrochemical processes and designing advanced energy storage devices with substantial capacity and considerable power density.

Toward Planar and Dendrite-Free Zn Electrodepositions by Regulating Sn-Crystal Textured Surface.

The propensity of Zn-metal anodes to form non-uniform or dendritic electrodeposits is bound up with the nature of the electrode surface. However, the effect of surface structure on the inherent nucleation and deposition of Zn is not yet well understood. Here, the surface structure of a Zn-metal anode is reconstructed with Sn-crystal textures via a facile chemical displacement reaction. Compared to the bare Zn, the high-affinity Zn binding sites of Sn afford lower deposition energy barrier, which promotes deposition kinetics. What is more, a Sn-textured surface with moderate Zn affinity but high average surface energy ensures a better wettability from the deposits, leading to the lateral growth of Zn crystals. The resultant Sn-textured Zn-metal anode exhibits an extremely low voltage hysteresis of 20 mV and achieves a prolonged cycling stability over 500 h cycles without dendrite formation. This work provides new insights into the crystal-texture-dependent Zn electrodeposition process and offers direction for direct surface texturing to better stabilize Zn-metal anodes with improved reversibility.

Operando Magnetometry Probing the Charge Storage Mechanism of CoO Lithium-Ion Batteries.

Cobalt oxide (CoO) is a promising electrode for high-energy-density Li-ion batteries (LIBs), where the charge storage is believed to take place solely during the electrochemical oxidation/reduction processes. However, this simple picture has been increasingly challenged by reported anomalously large storage capacities, indicating the existence of undiscovered extra charge reservoirs inside the system. Here, an advanced operando magnetometry technology is employed to monitor the magnetization variation of the CoO LIBs in real time and, in this particular system, it is clearly demonstrated that the anomalous capacity is associated with both the reversible formation of a spin capacitor and the growth of a polymeric film at low voltages. Furthermore, operando magnetometry provides direct evidence of the catalytic role of metallic Co in assisting the polymeric film formation. These critical findings help pave the way for better understanding of the charge storage mechanisms of transition-metal oxides and further utilizing them to design novel electrode materials.

Mobility-Fluctuation-Controlled Linear Positive Magnetoresistance in 2D Semiconductor Bi2O2Se Nanoplates.

Linear magnetoresistance is generally observed in polycrystalline zero-gap semimetals and polycrystalline Dirac semimetals with ultrahigh carrier mobility. We report the observation of positive and linear magnetoresistance in a single-crystalline semiconductor Bi2O2Se grown by chemical vapor deposition. Both Se-poor and Se-rich Bi2O2Se single-crystalline nanoplates display a linear magnetoresistance at high fields. The Se-poor Bi2O2Se exhibits a typical 2D conduction feature with a small effective mass of 0.032m0. The average transport Hall mobility, which is lower than 5500 cm2 V-1 s-1, is significantly reduced, compared with the ultrahigh quantum mobility as high as 16260 cm2 V-1 s-1. More interestingly, the pronounced Shubnikov-de Hass oscillations can be clearly observed from the very large and nearly linear magnetoresistance (>500% at 14 T and 2 K) in Se-poor Bi2O2Se. A close analysis of the results reveals that the large and linear magnetoresistance observed can be ascribed to the spatial mobility fluctuation, which is strongly supported by Fermi energy inhomogeneity in the nanoplate samples detected using an electrostatic force microscopy images and multiple frequencies in a Shubnikov-de Hass oscillation. On the contrary, the Se-rich Bi2O2Se exhibits a transport mobility (<300 cm2 V-1 s-1) much smaller than that observed in Se-poor samples and shows a much smaller linear magnetoresistance ratio (less than 150% at 14 T and 2 K). More strikingly, no Shubnikov-de Hass oscillations can be observed. Therefore, the linear magnetoresistance in Se-rich Bi2O2Se is governed by the average mobility rather than the mobility fluctuation.

Ultrahigh Frequency and Anti-Interference Optical-Mode Resonance with Biquadratic Coupled FeCoB/Ru/FeCoB Trilayers.

Microwave soft magnetic films (SMFs) are the key materials to effectively miniaturize and multifunctionalize the microwave electromagnetic components and devices. However, currently, single-layer SMFs encounter a frequency bottleneck at around 10 GHz. The ferromagnet/nonmagnetic spacer/ferromagnet sandwiched films with strong interlayer exchange coupling are possible solutions to break through that frequency limitation because they exhibit ultrahigh optical-mode (OM) resonance frequency frO up to 50 GHz, while the tiny permeability and the limited thickness are their own obstacles to overcome. In this study, biquadratic coupled FeCoB25nm/Ru0.25nm/FeCoB25nm sandwiched films with uniaxial magnetic anisotropy were deposited by a composition gradient sputtering method. Pure OM resonance with self-bias frO up to 18.21 GHz and a relative permeability µrO as high as 169 at the cut-off frequency was achieved. Moreover, both the frO and µrO remain unchanged in the magnetic field range of 0-80 Oe, indicating a strong anti-interference capability to small interference field. These results demonstrate that the biquadratic coupled OM resonance can solve the current frequency bottleneck of microwave SMFs by providing ultrahigh resonance frequency while maintaining considerable permeability, thus leading to potential applications of OM resonance in Ku-band microwave magnetic components.

Stress-Enhanced Interlayer Exchange Coupling and Optical-Mode FMR Frequency in Self-Bias FeCoB/Ru/FeCoB Trilayers.

Nowadays, the most popular method to increase ferromagnetic resonance (FMR) frequency ( fr) in self-bias soft magnetic films is to improve the anisotropy field HK. However, to push fr to higher frequencies only via raising HK becomes increasingly challenging because fr is already higher than 10 GHz by now. In this study, we fabricated a series of magnetically anisotropic FeCoB/Ru/FeCoB sandwich films possessing antiferromagnetic-like coupling and gradually increased uniaxial stress in the FeCoB sublayers from 52 to 110 MPa. It is quite remarkable that the acoustic mode of FMR gradually disappears, whereas the optical mode is enhanced in these structures. We observed simultaneous enhancement of HK and interlayer coupling field ( JIEC) with the uniaxial stress, which leads to a very pronounced optical-mode frequency increase from 8.67 to 11.62 GHz with a very sensitive stress response of 51 Hz/Pa. In contrast, the fr in a FeCoB single layer (acoustic mode) only varies from 3.47 to 5.05 GHz under similar stress. We believe that the strain-induced electron density variation of the Ru spacer's Fermi surface in the out-of-plane direction is responsible for the enhancement of JIEC. This study demonstrates that the antiferromagnetic coupling is a new route to achieve higher fr and provides the possibility of engineering and manipulating optical-mode resonance simply by controlling the interlayer coupling strength via stress.

Phonon engineering in proximity enhanced superconductor heterostructures.

In this research, we tailor the phonon density of states (DOS) in thin superconducting films to suppress quasiparticle losses. We examine a model system of a proximity-enhanced three-layered Al/Nb/Al heterostructure and show that the local quantized phonon spectrum of the ultrathin Al cladding layers in the heterostructure has a pronounced effect on the superconducting resonator's quality factors. Instead of a monotonic increase of quality factors with decreasing temperatures, we observe the quality factor reaches a maximum at 1.2 K in 5/50/5 nm Al/Nb/Al microstrip resonators, because of a quantized phonon ladder. The phonon DOS may be engineered to enhance the performance of quantum devices.

Valley precession and valley polarization in graphene with inter-valley coupling.

We theoretically investigate the valley precession and valley polarization in graphene under inter-valley coupling. Our results show that the inter-valley coupling can induce valley polarization in graphene and also precess valleys in real space in a manner similar to the Rashba spin-orbit interaction rotating spins. Moreover, using strain modulation, we can achieve high valley polarization with large valley-polarized currents. These findings provide a new way to create and manipulate valley polarization in graphene.

Edge states and quantum phase transition in graphene under in-plane effective exchange fields.

We investigated the edge states and quantum phase transition in graphene under an in-plane effective exchange field. The result shows that the combined effects of the in-plane effective exchange field and a staggered sublattice potential can induce zero-energy flat bands of edge states. Such flat-band edge states can evolve into helical-like ones in the presence of intrinsic spin-orbit coupling, with a unique spin texture. We also find that the bulk energy gap induced by the spin-orbit coupling and staggered sublattice potential can be closed and reopened with the in-plane effective exchange field, and the reopened bulk gap can be even larger than that induced by only the spin-orbit coupling and staggered sublattice potential, which is different from the case of an out-of-plane effective exchange field. The calculated spin-dependent Chern numbers suggest that the bulk gap closing and reopening is accompanied by a quantum phase transition from a trivial insulator phase across a metal phase into a spin-dependent quantum Hall phase.

Tunable Dirac points and high spin polarization in ferromagnetic-strain graphene superlattices.

Spin-dependent energy bands and transport properties of ferromagnetic-strain graphene superlattices are studied. The high spin polarization appears at the Dirac points due to the presence of spin-dependent Dirac points in the energy band structure. A gap can be induced in the vicinity of Dirac points by strain and the width of the gap is enlarged with increasing strain strength, which is beneficial for enhancing spin polarization. Moreover, a full spin polarization can be achieved at large strain strength. The position and number of the Dirac points corresponding to high spin polarization can be effectively manipulated with barrier width, well width and effective exchange field, which reveals a remarkable tunability on the wavevector filtering behavior.