Tunneling Transport Research Articles

Tunnel junctions based on interfacial two dimensional ferroelectrics

Van der Waals heterostructures have opened new opportunities to develop atomically thin (opto)electronic devices with a wide range of functionalities. The recent focus on manipulating the interlayer twist angle has led to the observation of out-of-plane room temperature ferroelectricity in twisted rhombohedral bilayers of transition metal dichalcogenides. Here we explore the switching behaviour of sliding ferroelectricity using scanning probe microscopy domain mapping and tunnelling transport measurements. We observe well-pronounced ambipolar switching behaviour in ferroelectric tunnelling junctions with composite ferroelectric/non-polar insulator barriers and support our experimental results with complementary theoretical modelling. Furthermore, we show that the switching behaviour is strongly influenced by the underlying domain structure, allowing the fabrication of diverse ferroelectric tunnelling junction devices with various functionalities. We show that to observe the polarisation reversal, at least one partial dislocation must be present in the device area. This behaviour is drastically different from that of conventional ferroelectric materials, and its understanding is an important milestone for the future development of optoelectronic devices based on sliding ferroelectricity.

Elucidating the Role of O2 Uncoupling for the Adaptation of Bacterial Biodegradation Reactions Catalyzed by Rieske Oxygenases.

Oxygenation of aromatic and aliphatic hydrocarbons by Rieske oxygenases is the initial step of various biodegradation pathways for environmental organic contaminants. Microorganisms carrying Rieske oxygenases are able to quickly adapt their substrate spectra to alternative carbon and energy sources that are structurally related to the original target substrate, yet the molecular events responsible for this rapid adaptation are not well understood. Here, we evaluated the hypothesis that reactive oxygen species (ROS) generated by unproductive activation of O2, the so-called O2 uncoupling, in the presence of the alternative substrate exert a selective pressure on the bacterium for increasing the oxygenation efficiency of Rieske oxygenases. To that end, we studied wild-type 2-nitrotoluene dioxygenase from Acidovorax sp. strain JS42 and five enzyme variants that have evolved from adaptive laboratory evolution experiments with 3- and 4-nitrotoluene as alternative growth substrates. The enzyme variants showed a substantially increased oxygenation efficiency toward the new target substrates concomitant with a reduction of ROS production, while mechanisms and kinetics of enzymatic O2 activation remained unchanged. Structural analyses and docking studies suggest that amino acid substitutions in enzyme variants occurred at residues lining both substrate and O2 transport tunnels, enabling tighter binding of the target substrates in the active site. Increased oxygenation efficiencies measured in vitro for the various enzyme (variant)-substrate combinations correlated linearly with in vivo changes in growth rates for evolved Acidovorax strains expressing the variants. Our data suggest that the selective pressure from oxidative stress toward more efficient oxygenation by Rieske oxygenases was most notable when O2 uncoupling exceeded 60%.

Research on rockburst proneness evaluation based on interpretation of drilling parameters

Rockburst is one of the common geological disasters in underground engineering. Rockburst proneness evaluation is the premise of rockburst disaster prevention and control. It is an effective method to evaluate rockburst proneness by brittleness index. The traditional brittleness index testing requires coring the surrounding rock in the field and transporting it to the laboratory for testing. The testing process is inefficient and disconnected from the in-situ environment. The effective in-situ and accurate test of brittleness index has become a challenge. Digital drilling testing of rock mass is a new approach to solve the above problems and future research direction. The study explore a rockburst proneness evaluation method based on the interpretation of real-time drilling parameters. The key of this method is to establish the quantitative relationship model between the brittleness index and drilling parameters. Digital drilling tests on different rock types were conducted using the rock intelligent rotary cutting testing system (RCT system). The quantitative relationship between drilling parameters and rock strength parameters was analyzed. The drilling test model of rock equivalent brittleness index (DP-EBI model) is established. The verification test results show that the difference rate between the rock brittleness index with drilling test and indoor test is 11.8%. On this basis, the testing results of five rockburst evaluation methods, including equivalent brittleness index EBI, energy impact index ACF, potential energy of elastic strain PES, brittleness index modified BIM and dynamic failure time DT were compared. The effectiveness of using drilling parameters to evaluate rockburst proneness is verified. This study can provide a theoretical and methodological basis for the in-situ detection and evaluation of rockburst proneness and grade in underground engineering fields, such as mine roadways, transportation tunnels, and hydraulic tunnels.

Detection methods for strength deterioration and structural characteristics of fractured rock based on digital drilling

Fractures ubiquitously exist in strata, and large-scale fractures can cause low bearing capacity and poor stability in rock masses and can sometimes lead to hazards such as roof falls and collapses in mines and tunnels. The foundation of the control of surrounding rocks and effective prevention of such hazards is to be able to accurately determine the structural characteristics of fractures and strength parameters of rocks. Traditionally, testing is carried out mainly through indoor compression tests and borehole inspection, which require drilling of the surrounding rock on site and core testing indoors. The effective in situ and accurate detection of the structure and strength properties of surrounding rock has become a challenge. Digital drilling testing of rock mass is a new approach to solve the above problems and future research direction. In this study, a multifunctional rock mass digital drilling test system is used to perform tests on different types of fractured rocks. The response of drilling parameters to fracture parameters is analysed, and a strength deterioration evaluation index for fractured rock based on drilling parameters is established. Then, the response mechanism of the strength deterioration rate while drilling in the fracture zone is defined, and a model for identifying fracture parameters based on drilling is established. Furthermore, an in situ detection method for fractured rock properties based on digital drilling is proposed. The results of the validation test show that the average difference ratio between the equivalent compressive strength measured by the drilling test and the laboratory compressive test is 3.97 %. The strength degradation of the fractured rock is significant, with a maximum strength degradation rate of 82.1 % obtained through drilling. The average identification accuracies of the fracture position and width are 2.56 mm and 0.85 mm, respectively. The identification accuracy of rock properties while drilling is high, which proves the effectiveness of the prediction model while drilling. This study can provide a theoretical and methodological basis for the accurate in situ prediction of rock properties in underground engineering fields, such as mine roadways, transportation tunnels, and hydraulic tunnels.

Electronic inhomogeneity and phase fluctuation in one-unit-cell FeSe films

One-unit-cell FeSe films on SrTiO3 substrates are of great interest owing to significantly enlarged pairing gaps characterized by two coherence peaks at ±10 meV and ±20 meV. In-situ transport measurement is desired to reveal novel properties. Here, we performed in-situ microscale electrical transport and combined scanning tunneling microscopy measurements on continuous one-unit-cell FeSe films with twin boundaries. We observed two spatially coexisting superconducting phases in domains and on boundaries, characterized by distinct superconducting gaps (Δ1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\Delta }_{1}$$\\end{document}~15 meV vs. Δ2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\Delta }_{2}$$\\end{document}~10 meV) and pairing temperatures (Tp1~52.0 K vs. Tp2~37.3 K), and correspondingly two-step nonlinear V~Iα\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$V \\sim {I}^{\\alpha }$$\\end{document} behavior but a concurrent Berezinskii–Kosterlitz–Thouless (BKT)-like transition occurring at TBKT\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${T}_{{{{{{\\rm{BKT}}}}}}}$$\\end{document}~28.7 K. Moreover, the onset transition temperature Tconset\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${T}_{{{{{{\\rm{c}}}}}}}^{{{{{{\\rm{onset}}}}}}}$$\\end{document}~54 K and zero-resistivity temperature Tczero\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${T}_{{{{{{\\rm{c}}}}}}}^{{{{{{\\rm{zero}}}}}}}$$\\end{document}~31 K are consistent with Tp1 and TBKT\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${T}_{{{{{{\\rm{BKT}}}}}}}$$\\end{document}, respectively. Our results indicate the broadened superconducting transition in FeSe/SrTiO3 is related to intrinsic electronic inhomogeneity due to distinct two-gap features and phase fluctuations of two-dimensional superconductivity.

Variability of entropy force and its coupling with electrostatic and steric hindrance interactions

We investigated the effective interaction potential (EIP) between charged surfaces in solvent comprised of dipole dimer molecules added with a certain amount of ionic liquid. Using classical density functional theory, the EIP is calculated and decoupled into entropic and energy terms. Unlike the traditional Asakura–Oosawa (AO) depletion model, the present entropic term can be positive or negative, depending on the entropy change associated with solvent molecule migration from bulk into slit pore. This is determined by pore congestion and disruption of the bulk dipole network. The energy term is determined by the free energy associated with hard-core repulsion and electrostatic interactions between surface charges, ion charges, and polarized charges carried by the dipole dimer molecules. The calculations in this article clearly demonstrate the variability of the entropy term, which contrasts sharply with the traditional AO depletion model, and the corrective effects of electrostatic and spatial hindrance interactions on the total EIP; we revealed several non-monotonic behaviors of the EIP and its entropic and energy terms concerning solvent bulk concentration and solvent molecule dipole moment; additionally, we demonstrated the promoting effect of dipolar solvent on the emergence of like-charge attraction, even in 1:1 electrolyte solutions. The microscopic origin of the aforementioned phenomena was analyzed to be due to the non-monotonic change of dipolar solvent adsorption with dipole moment under conditions of low solution dielectric constant. The present findings offer novel approaches and molecular-level guidance for regulating the EIP. This insight has implications for understanding fundamental processes in various fields, including biomolecule-ligand binding, activation energy barriers, ion tunneling transport, as well as the formation of hierarchical structures, such as mesophases, micro-, and nanostructures, and beyond.

Contribution of strong electron-phonon interaction in the transport properties of La0.8Ca0.2Mn0.5Ni0.5O3 system

La0.8Ca0.2Mn0.5Ni0.5O3 NTC (negative thermal coefficient) thermo-sensitive material was prepared using a conventional solid-state reaction method. From the structural results, we found that the material is pure and crystallizes in the orthorhombic structure with a Pnma space group. It is found that the La0.8Ca0.2Mn0.5Ni0.5O3 ceramic can be used as an NTC thermistor compound in specific temperature sensors and attenuators. Based on Holsten's theory, detailed electrical investigations concerning the nature of the activated small polaron hopping mechanism were reported. The temperature dependence of the DC conductance was used to determine the electrical conduction processes that govern the transport properties of La0.8Ca0.2Mn0.5Ni0.5O3. Hence, the DC mechanisms exhibit changes from the variable range hopping at very low temperatures to the non-adiabatic small polaronic hopping at T = 210 K. In the intermediate temperature range, the semiconductor behavior of La0.8Ca0.2Mn0.5Ni0.5O3 was attributed to the contribution of the tunneling transport process. At various temperatures, the conductance spectra were discussed based on Jonscher and Bruce's laws. Contributions of the overlapping-large-polaron-tunneling, the correlated barrier hopping, the quantum mechanical tunneling, and the non-overlapping small polaron tunneling mechanisms to the transport properties were observed in the dispersive region of the conductance spectra. In addition, Summerfield scaling and corrected Summerfield scaling approaches prove that the charge mobility is temperature-dependent. The positive value of the correction parameter α = 1.2 confirms the presence of interactions in the studied sample.

Comparative Evaluation of VXLAN with Traditional Overlay Network Protocols

This article examines various network virtualization technologies, including Virtual Extensible LAN (VXLAN), as well as overlay network protocols such as VXLAN-EVPN (Ethernet VPN) and VXLAN-LISP (Locator/Identifier Separation Protocol). These protocols play a crucial role in improving the scalability and flexibility of big cloud computing infrastructures. While each of these technologies can be employed to expand a Layer 2 connection across an already established network, they possess unique qualities and applications. The objective is to offer a comprehensive comprehension of these technologies and their suitability in diverse network contexts.VXLAN-EVPN has higher performance in terms of encapsulation speed and reduced packet overhead, rendering it highly suitable for high-speed and large-scale deployments. Conversely, VXLAN-LISP demonstrates superior network latency and interoperability, offering benefits in multi-tenant and geographically distributed networks. VXLAN can be combined with other widely used overlay network protocols, including Generic Network Virtualization Encapsulation (GENEVE), Stateless Transport Tunneling (STT), and Network Virtualization using Generic Routing Encapsulation (NVGRE). The objective is to offer a comprehensive comprehension of these technologies and their suitability in diverse network contexts.

Structural and optical properties of position-controlled n-ZnO nanowire arrays: Potential applications in optoelectronics

Highly position-controlled ZnO nanowire (NW) arrays and nanowire-cluster (NW–C) arrays are grown on mask-patterned gallium nitride (GaN) substrates by hydrothermal method. Electroluminescence (EL) emissions with blue-violet light at forward-bias(fb) voltage, EL emissions with yellow light at reverse-bias(rb) voltage, and EL emission at both rb voltages and rb voltages were achieved by the adjustment of the size of the heterojunction interface between wire arrays and film. The high rb current is attributed to electron tunneling transport edge effect via a narrow tunnel barrier. The obtained results highlight that the EL characteristics of ZnO NWs can be tuned and controlled through the size of the heterojunction interface between wire arrays and film. Besides, the nonplanar heterogeneous structure of ZnO NW arrays/GaN film also shown a great spectral response characteristic in the ultraviolet(UV) band, which proves that the structure of is worthy of being studied to achieve high performance UV photodetectors.

Joint Mechanism (Tunneling and Thermionic Emission) for Improved Performance of a Dielectric Modulated Transistor Biosensor

The manuscript deals with a novel biosensor structure and reports the effects of including thermionic emission in an electrically doped Tunnel FET. It comprises a comparative analysis between two biosensors based on a pure tunnelling transistor and a transistor which combines the tunnelling and thermionic emission carrier transport in the same device. The manuscript first discusses the physics of Tunnel FET when vertical thermionic emission is included with horizontal tunnelling through an additional electron source (AES). Subsequently, the biosensor is designed using the combined mechanism structure a comparative analysis of biosensors is done in terms of various DC and RF parameters for different biomolecules of proteins. Moreover, workfunction engineering is implemented to the combined mechanism biosensor and sensitivity is analyzed by drain current and transconductance.

Structure of antiviral drug bulevirtide bound to hepatitis B and D virus receptor protein NTCP

Cellular entry of the hepatitis B and D viruses (HBV/HDV) requires binding of the viral surface polypeptide preS1 to the hepatobiliary transporter Na+-taurocholate co-transporting polypeptide (NTCP). This interaction can be blocked by bulevirtide (BLV, formerly Myrcludex B), a preS1 derivative and approved drug for treating HDV infection. Here, to elucidate the basis of this inhibitory function, we determined a cryo-EM structure of BLV-bound human NTCP. BLV forms two domains, a plug lodged in the bile salt transport tunnel of NTCP and a string that covers the receptor’s extracellular surface. The N-terminally attached myristoyl group of BLV interacts with the lipid-exposed surface of NTCP. Our structure reveals how BLV inhibits bile salt transport, rationalizes NTCP mutations that decrease the risk of HBV/HDV infection, and provides a basis for understanding the host specificity of HBV/HDV. Our results provide opportunities for structure-guided development of inhibitors that target HBV/HDV docking to NTCP.

Electrical characterization of multi-gated WSe2/MoS2 van der Waals heterojunctions

Vertical stacking of different two-dimensional (2D) materials into van der Waals heterostructures exploits the properties of individual materials as well as their interlayer coupling, thereby exhibiting unique electrical and optical properties. Here, we study and investigate a system consisting entirely of different 2D materials for the implementation of electronic devices that are based on quantum mechanical band-to-band tunneling transport such as tunnel diodes and tunnel field-effect transistors. We fabricated and characterized van der Waals heterojunctions based on semiconducting layers of WSe2 and MoS2 by employing different gate configurations to analyze the transport properties of the junction. We found that the device dielectric environment is crucial for achieving tunneling transport across the heterojunction by replacing thick oxide dielectrics with thin layers of hexagonal-boronnitride. With the help of additional top gates implemented in different regions of our heterojunction device, it was seen that the tunneling properties as well as the Schottky barriers at the contact interfaces could be tuned efficiently by using layers of graphene as an intermediate contact material.

Room‐temperature tunable tunneling magnetoresistance in Fe3GaTe2/WSe2/Fe3GaTe2 van der Waals heterostructures

AbstractThe exceptional properties of two‐dimensional (2D) magnet materials present a novel approach to fabricate functional magnetic tunnel junctions (MTJ) by constructing full van der Waals (vdW) heterostructures with atomically sharp and clean interfaces. The exploration of vdW MTJ devices with high working temperature and adjustable functionalities holds great potential for advancing the application of 2D materials in magnetic sensing and data storage. Here, we report the observation of highly tunable room‐temperature tunneling magnetoresistance through electronic means in a full vdW Fe3GaTe2/WSe2/Fe3GaTe2 MTJ. The spin valve effect of the MTJ can be detected even with the current below 1 nA, both at low and room temperatures, yielding a tunneling magnetoresistance (TMR) of 340% at 2 K and 50% at 300 K, respectively. Importantly, the magnitude and sign of TMR can be modulated by a DC bias current, even at room temperature, a capability that was previously unrealized in full vdW MTJs. This tunable TMR arises from the contribution of energy‐dependent localized spin states in the metallic ferromagnet Fe3GaTe2 during tunnel transport when a finite electrical bias is applied. Our work offers a new perspective for designing and exploring room‐temperature tunable spintronic devices based on vdW magnet heterostructures.

High-temperature photoelectronic transport behavior of n-TiO2 nanorod clusters/p-degenerated boron-doped diamond heterojunction

N-TiO2 nanorod clusters (Ncs)/p-degenerated boron-doped diamond (n-TiO2 Ncs/p-DBDD) film heterojunction was prepared by hydrothermal method, and the photoelectric properties depending on temperature dependence were tested. Three distinct emission peaks of 402 nm, 429 nm and 454 nm were detected by the photoluminescence (PL) test under 355 nm ultraviolet light and excited in the blue-green region light. The heterojunction exhibited good rectification characteristics and thermal stability from room temperature to 180 °C. The forward current first decreases and then increases with increasing temperature. The 160 °C is considered to be the ideal high temperature for the best performance of the heterojunction, with the rectification ratio reaching 20.667. The carrier transport mechanisms and tunneling process of n-TiO2 Ncs/p-DBDD heterojunction with temperature are analyzed in detail through the established band structure diagram. This study provides an effective way method for the potential development of high-temperature stable optoelectronic devices.

Molecular insights into ferric-siderophore transport by the putative TonB-dependent transporter in Mycobacterium tuberculosis

Iron acquisition is critical to the virulence of Mycobacterium tuberculosis (Mtb), the causative agent of tuberculosis. To acquire iron within the host, Mtb secretes siderophores that chelate iron with high affinity. Siderophores scavenge iron from host cells using TonB-dependent transporters like FecA. We investigated molecular mechanisms of FecA-mediated ferric-siderophore transport in Mtb. Molecular docking and molecular dynamics simulations revealed a series of interactions between ferric siderophores and FecA. The initial binding occurs at a pocket located on the extracellular surface of FecA. The ligand then migrates deeper through the transport tunnel to a subsequent binding site, aided by conformational changes in FecA that expand the tunnel diameter. We observed the key roles of precise positioning of extracellular loops in the outer membrane barrel and plug domains in the optimal ligand binding and transport. Transport of ferric–siderophore complex into Mtb follows an induced fit model, with ligand interaction eliciting 2–10 Å shifts in the barrel and plug regions. By revealing the conformational dynamics enabling iron import, these findings provide molecular-level insights into a metal ion uptake mechanism in Mtb. Iron acquisition is essential for Mtb pathogenesis, so this work may inform novel therapeutic strategies that disrupt siderophore uptake pathways. Communicated by Ramaswamy H. Sarma

Sputtering pressure dependence of microstructure and magnetoresistance properties of non-uniform Co–ZnO nanocomposite film

Co-ZnO metal–semiconductor nanocomposite films have become the focus of attention in recent years since their magnetoresistance (MR) effect at room temperature (RT). In this study, non-uniform Co-ZnO nanocomposite films were prepared by magnetron co-sputtering method. With sputtering pressure increasing, the formation of ferromagnetic Co clusters is suppressed effectively, and the metallic-state superparamagnetic Co particles are dispersed, which form the tunneling transport paths in the Co-ZnO films at high Co content. As the sputtering pressure increases from 0.3 Pa to 1.2 Pa, the RT -MR value of the films increases from 0.41 % to 11.85 %, and the saturation magnetization of the films rises from 6.3 kGs to 7.3 kGs and then decreases to 6.7 kGs. It is noteworthy that the low-field MR field sensitivity at 1000 Oe is enhanced by about 10 times from 0.5 Pa to 1.2 Pa. This provides a reference for the application of low-magnetic field detectors.

Klein tunneling degradation and enhanced Fabry-Pérot interference in graphene/h-BN moiré-superlattice devices

Hexagonal boron-nitride (h-BN) provides an ideal substrate for supporting graphene devices to achieve fascinating transport properties, such as Klein tunneling, electron optics and other novel quantum transport phenomena. However, depositing graphene on h-BN creates moiré superlattices, whose electronic properties can be significantly manipulated by controlling the lattice alignment between layers. In this work, the effects of these moiré structures on the transport properties of graphene are investigated using atomistic simulations. At large misalignment angles (leading to small moiré cells), the transport properties (most remarkably, Klein tunneling) of pristine graphene devices are conserved. On the other hand, in the nearly aligned cases, the moiré interaction induces stronger effects, significantly affecting electron transport in graphene. In particular, Klein tunneling is significantly degraded. In contrast, strong Fabry-Pérot interference (accordingly, strong quantum confinement) effects and non-linear I-V characteristics are observed. P-N interface smoothness engineering is also considered, suggesting as a potential way to improve these transport features in graphene/h-BN devices.

Ultrathin Reed Membranes: Nature's Intimate Ion‐Regulation Skins Safeguarding Zinc Metal Anodes in Aqueous Batteries

AbstractThe practical realization of aqueous zinc‐ion batteries relies crucially on effective interphases governing Zn electrodeposition chemistry. In this study, an innovative solution by introducing an ultrathin (≈2 µm) biomass membrane as an intimate artificial interface, functioning as nature's ion‐regulation skin to protect zinc metal anodes is proposed. Capitalizing on the inherent properties of natural reed membrane, including multiscale ion transport tunnels, abundant ─OH groups, and remarkable mechanical integrity, the reed membrane demonstrates efficacy in regulating uniform and rapid Zn2+ transport, promoting desolvation, and governing Zn (002) plane electrodeposition. Importantly, a unique in situ electrochemical Zn─O bond formation mechanism between the reed membrane and Zn electrode upon cycling is elucidated, resulting in a robustly adhered interface covering on the zinc anode surface, ultimately ensuring remarkable dendrite‐free and highly reversible Zn anodes. Consequently, the approach achieves a prolonged cycle life for over 1450 h at 3 mA cm−2/1.5 mAh cm−2 in symmetric Zn//Zn cells. Moreover, exceptional cyclic performance (88.95%, 4000 cycles) is obtained in active carbon‐based cells with an active mass loading of 5.8 mg cm−2. The approach offers a cost‐effective and environmentally friendly strategy for achieving stable and reversible zinc anodes for aqueous batteries.

Electrostatically Shielded Transportation Enabling Accelerated Na+ Diffusivity in High‐Performance Fluorophosphate Cathode for Sodium‐Ion Batteries

AbstractA typical polyanionic based material Na3V2(PO4)2O2F (Na3VPO2F) attracts much interest as a cathode for large‐scale sodium‐ion batteries in consideration of its stable structure and remarkable energy density. Nevertheless, the large coulombic attraction and repulsion suffered by the mobile Na+ from structural anions and surrounding Na+, respectively, result in a torpid reaction kinetics and inferior rate capability. Herein, Br−‐doped and Na+ vacancy preinstalled Na3−yVPO2−xBrxF is prepared to dilute the charges on and inside the Na+ transportation tunnel. In virtue of density functional theory analysis, Na3−yVPO2−xBrxF reveals a reduction in the bandgap and an increase in electronic conductivity. Meanwhile, the almost electrostatically shielded tunnel in Na3−yVPO2−xBrxF alleviates the coulombic hindrance imposed on Na+ during its (de)intercalation, which demonstrates a Na+ diffusivity about five times higher than that of Na3VPO2F. Consequently, the Na3−yVPO2−xBrxF cathode shows a superior rate capacity of 77.7 mAh g−1 under 50 C and great cycling property corresponding to a high capacity retention of 94.4% over 800 cycles at 10 C. The assembled Na3−yVPO2−xBrxF//hard‐carbon sodium‐ion full‐cell presents excellent specific energy/power (226 Wh kg−1@15424.2 W kg−1) as well as outstanding long‐term cyclic stability over 1000 cycles at 5 C.

Enabling Further Organic Electrolyte Infiltration of Cellulose-Based Separators via Defect-Rich Polypyrrole Modification for High Sodium Ion Transport in Sodium Metal Batteries.

Sodium metal batteries (SMBs) have high-density and cost-effective characteristics as one of the energy storage systems, but uncontrollable dendrite growth and poor rate performance still hinder their practical applications. Herein, a nitrogen-rich modified cellulose separator with released abundant ion transport tunnels in organic electrolyte was synthesized by in situ polymerization of polypyrrole, which is based on the high permeability of cellulose in aqueous solution and the interfacial interaction between cellulose and polypyrrole. Meanwhile, the introduction of abundant structural defects such as branch chains, oxygen-containing functional groups, and imine-like structure to disrupt polypyrrole conjugation enables the utilization of conductive polymers in composite separator applications. With the electrolyte affinity surface on, the modified separator exhibits reinforced electrolyte uptake (254%) and extended electrolyte wettability, thereby leading to accelerated ionic conductivity (2.77 mS cm-1) and homogeneous sodium deposition by facilitating the establishment of additional pathways for ion transport. Benefiting from nitrogen-rich groups, the polypyrrole-modified separator demonstrates selective Na+ transport by the data of improved Na+ transference number (0.62). Owing to the above advantages, the battery assembled with the modified separators exhibits outstanding rate performance and prominent capacity retention two times that of the pristine cellulose separator at a high current density under the condition of fluorine-free electrolyte.