Ion Transport Behavior Research Articles

Microstructure and chloride transport of aeolian sand concrete under long-term natural immersion

Abstract River sand was consumed in large quantities, and alternatives to river sand were urgently needed. There are a large number of natural resources of aeolian sand in western China. Aeolian sand was prepared into aeolian sand concrete (ASC). It can greatly reduce the consumption of river sand and inhibit the process of desertification to protect the environment. ASC is a new type of concrete material prepared by using aeolian sand as fine aggregate. To clarify the chloride ion transport behaviour in the ASC under long-term natural immersion, the aeolian sand was 100% substituted for the river sand to prepare the full ASC with three water–binder ratios. The ASC was naturally immersed in 3 and 6% NaCl solutions for a long time, and nuclear magnetic resonance and microscopic scanning electron microscopy techniques were used. The change rule of chloride ion content at different depths of the ASC was studied, and its microstructure characteristics under different erosion times were analysed. The results showed that the free chloride ion concentration at different depths of the ASC increased with increasing water–binder ratio, immersion time, and chloride concentration. After soaking in the salt solution, the hydration products in the ASC reacted with chloride ions to form Friedel salt, which filled the internal pores and microcracks of the ASC, improved its interface transition zone structure, and increased the compactness of the test piece. The porosity of the three groups of ASC with different water–binder ratios decreased by 0.95, 1.03, and 1.15% after soaking in 6% salt solution for 12 m. To study the diffusion law of chloride ions in ASC, combined with influencing factors such as temperature, humidity, D value, deterioration effect and chloride ion combination, Fick’s second law was modified, and a chloride ion diffusion model of ASC with high accuracy was established, with a fitting correlation number above 0.93, which provided a reference for the research and application of ASC in saline areas.

Ion Transport Behavior in van der Waals Gaps of 2D Materials.

2D materials, with advantages of atomic thickness and novel physical/chemical characteristics, have emerged as the vital building blocks for advanced lamellar membranes which possess promising potential in energy storage, ion separation, and catalysis. When 2D materials are stacked together, the van der Waals (vdW) force generated between adjacent layered nanosheets induces the construction of an ordered lamellar membrane. By regulating the interlayer spacing down to the nanometer or even sub-nanometer scale, rapid and selective ion transport can be achieved through such vdW gaps. The further improvement and application of qualified 2D materials-based lamellar membranes (2DLMs) can be fulfilled by the rational design of nanochannels and the intelligent micro-environment regulation under different stimuli. Focusing on the newly emerging advances of 2DLMs, in this review, the common top-down and bottom-up synthesis approaches of 2D nanosheets and the design strategy of functional 2DLMs are briefly introduced. Two essential ion transport mechanisms within vdW gaps are also involved. Subsequently, the responsive 2DLMs based on different types of external stimuli and their unique applications in nanofluid transport, membrane-based filters, and energy storage are presented. Based on the above analysis, the existing challenges and future developing prospects of 2DLMs are further proposed.

Superspreading‐Confined Assembly of Oriented 2D MOF Membranes for Biomimetic Cation‐Regulated Ion Transport

AbstractInspired by biological channels, metal‐organic framework (MOF) membranes with sub‐nanometer sized channels offer an ideal platform to construct high‐performance artificial nanofluidic system. However, fabricating long‐range ordered MOF membranes is still a significant challenge. Herein, a superspreading‐confined assembly method is developed to prepare large‐scale oriented 2D MOF (Zn‐TCPP (TCPP = meso‐tetra(4‐carboxyphenyl) porphine)) membranes. The superspreading of reactant liquid under oil phase to form liquid layer plays a critical role in membrane formation, which provides a dynamic confined space for layered assembly of Zn‐TCPP nanosheets. Accompanied with solvent diffusion, such liquid layer is completely converted into <001>‐oriented MOF membrane with controlled thickness. The prepared membrane exhibits distinct divalent cation (Mx2+)‐regulated ion transport behavior as that demonstrated in biological channels: K+ flux can be precisely adjusted by anchoring diverse Mx2+ ions to binding sites, which is appealing in designing high‐performance nanofluidic iontronics. Moreover, similar strategies can be employed to fabricate other MOF membranes (such as Hf‐BTB (BTB = 1,3,5‐tris(4‐carboxyphenyl)benzene) and Ni‐TCPE (TCPE = tetrakis(4‐carboxyphenyl)ethylene)), indicating the broad applicability of this method in 2D membrane fabrication.

Archaea-Inspired Switchable Nanochannels for On-Demand Lithium Detection by pH Activation.

With the rapid development of the lithium ion battery industry, emerging lithium (Li) enrichment in nature has attracted ever-growing attention due to the biotoxicity of high Li levels. To date, fast lithium ion (Li+) detection remains urgent but is limited by the selectivity, sensitivity, and stability of conventional technologies based on passive response processes. In nature, archaeal plasma membrane ion exchangers (NCLX_Mj) exhibit Li+-gated multi/monovalent ion transport behavior, activated by different stimuli. Inspired by NCLX_Mj, we design a pH-controlled biomimetic Li+-responsive solid-state nanochannel system for on-demand Li+ detection using 2-(2-hydroxyphenyl)benzoxazole (HPBO) units as Li+ recognition groups. Pristine HPBO is not reactive to Li+, whereas negatively charged HPBO enables specific Li+ coordination under alkaline conditions to decrease the ion exchange capacity of nanochannels. On-demand Li+ detection is achieved by monitoring the decline in currents, thereby ensuring precise and stable Li+ recognition (>0.1 mM) in the toxic range of Li+ concentration (>1.5 mM) for human beings. This work provides a new approach to constructing Li+ detection nanodevices and has potential for applications of Li-related industries and medical services.

Nano-Confined Effect and Heterojunction Promoted Exciton Separation for Light-Boosted Osmotic Energy Conversion.

The osmotic energy conversion properties of biomimetic light-stimulated nanochannels have aroused great interest. However, the power output performance is limited by the low light-induced current and energy conversion efficiency. Here, nanochannel arrays with simultaneous modification of ZnO and di-tetrabutylammonium cis-bis(isothiocyanato)bis(2,20-bipyridyl-4,40-dicarboxylato) ruthenium (II) (N719) onto anodic aluminum oxide (AAO) to combine the nano-confined effect and heterojunction is designed, which demonstrate rectified ion transport behavior due to the asymmetric composition, structure and charge. High cation selectivity and ion flux contribute to the high power density of ≈7.33Wm-2 by mixing artificial seawater and river water. Under light irradiation, heterojunction promoted the production and separation of exciton, enhanced cation selectivity, and improved the utilization efficiency of osmotic energy, providing a remarkable power density of ≈18.49Wm-2 with an increase of 252% and total energy conversion efficiency of 30.43%. The work opens new insights into the biomimetic nanochannels for high-performance energy conversion.

Biomimetic construction of smart nanochannels in covalent organic framework membranes for efficient ion separation

Smart nanochannels can regulate ion transport behavior by external stimulus and display precise ion selectivity in biological membrane systems, but constructing artificial membranes with responsive and tunable channel remains a severe challenge. Herein, smart covalent organic framework (COF) membranes decorated with photo-responsive azobenzene derivatives (COF-Azo) were fabricated by a biomimetic nanochannel modulation (BNM) strategy, endowing membranes with charged and switchable sub-nanochannels. Under different wavelength of light, the smart COF-Azo membranes simultaneously exhibited outstanding mono/monovalent and mono/divalent ion selectivity (K+/Li+ ideal selectivity of 17.9 and Li+/Mg2+ ideal selectivity of 24.9) via closing and opening channels. The conversion of effective pore size at angstrom level is realized by photoisomerization of azobenzene. After several photoswitch cycles, the smart membranes still maintained K+/Li+ selectivity of 6.1 and Li+/Mg2+ selectivity of 20.7 in mixed salt solution, exhibiting great potentials in lithium extraction. This work may blaze a trail in constructing photo-responsive nanochannel membranes for energy-efficient ion separation.

Regulating ion transport behaviors toward dendrite-free potassium metal batteries: recent advances and perspectives

Regulating ion transport behaviors toward dendrite-free potassium metal batteries: recent advances and perspectives

Channel engineering strategy of precisely modified MOF/nanofiber composite separator for advanced aqueous zinc ion batteries

As the combination of metal-organic framework (MOF) materials with adjustable channels and flexible polymeric matrix, MOF/nanofiber composite separators enable the controllable ion transport behavior, which offers promising candidates for developing novel battery separators. In this study, series MOF functionalized electrospun polyacrylonitrile nanofiber separators were successfully developed via a precisely surface grafting strategy and then served as the separators for highly efficient aqueous zinc (Zn)-ion batteries (ZIBs). Moreover, channel engineering was developed by placing amino (MOF-N) and sulfonic acid groups (MOF-NS) on the channel surface of UIO-66, which then effectively promoted the ion transport progress. In particular, the resultant MOF-NS shows an excellent ionic conductivity (22.81 mS cm−1), improved Zn2+ transference number (0.78), and outstanding cyclic durability. These enhanced properties can be contributed by the effectively promoted dissociation of zinc salts and desolvation processes of hydrated Zn ions through strong ion-dipole interactions, as confirmed by the theoretical simulations. Our work demonstrates the great importance of channel engineering in modifying porous MOFs materials and the strong power of the precisely modified MOF/nanofiber separators in regulating ion transmission behavior and thus offers a promising separator candidate for high performance aqueous ZIBs.

Surface Roughness Effects on Confined Nanoscale Transport of Ions and Biomolecules.

Biological channels, especially membrane proteins, play a crucial role in metabolism, facilitating the transport of nutrients and other materials across cell membranes in a bio-electrolyte environment. Artificial nanopores are employed to study ion and biomolecule transport behavior inside. While the non-specific interaction between the nanopore surface and transport targets has garnered significant attention, the impact of surface roughness is overlooked. In this study, Nanopores with different levels of inner surface roughness is created by adjusting the FIB (Focus Ion Beam) fabrication parameters. Experiments and molecular dynamics (MD) simulations are employed to demonstrate that greater roughness results from larger FIB beam currents and shorter processing times. Lower roughness increases the capture rate of biomolecules, while greater roughness enhances the normalized blockade current (ΔI/I0 ). The phenomenon of rougher nanopores are attributed to a barrier-dominated capture mechanism and more likely to induce DNA folding. This transport barrier exists in rough nanopores by utilizing steer molecular dynamics (SMD) simulations to investigate the force profile of a dA10 DNA molecule during translocation is demonstrated. This work illustrates how surface roughness influences the ionic current features and the translocation of biomolecules, paving a new way for tunning the molecule transport in nanopores.

Frameworked electrolytes: Ionic transport behavior and high mobility for solid state batteries

AbstractAll solid‐state batteries (ASSBs) are the holy grails of rechargeable batteries, where extensive searches are ongoing in the pursuit of ideal solid‐state electrolytes. Nevertheless, there is still a long way off to the satisfactorily high (enough) ionic conductivity, long‐term stability and especially being able to form compatible interfaces with the solid electrodes. Herein, we have explored ionic transport behavior and high mobility in the sub‐nano pore networks in the framework structures. Macroscopically, the frameworked electrolyte behaves as a solid, and however in the (sub)‐nano scales, the very limited number of solvent molecules in confinement makes them completely different from that in liquid electrolyte. Differentiated from a liquid‐electrolyte counterpart, the interactions between the mobile ions and surrounding molecules are subject to dramatic changes, leading to a high ionic conductivity at room temperature with a low activation energy. Li+ ions in the sub‐nano cages of the network structure are highly mobile and diffuse rather independently, where the rate‐limiting step of ions crossing cages is driven by the local concentration gradient and the electrostatic interactions between Li+ ions. This new class of frameworked electrolytes (FEs) with both high ionic conductivity and desirable interface with solid electrodes are demonstrated to work with Li‐ion batteries, where the ASSB with LiFePO4 shows a highly stable electrochemical performance of over 450 cycles at 2°C at room temperature, with an almost negligible capacity fade of 0.03‰ each cycle. In addition, the FE shows outstanding flexibility and anti‐flammability, which are among the key requirements of large‐scale applications.image

In Situ Growth of MOF-303 Membranes onto Porous Anodic Aluminum Oxide Substrates for Harvesting Salinity-Gradient Energy.

As an emerging metal-organic framework (MOF) material in recent years, the MOF-303 membrane has shown great potential applications in seawater desalination, dehydration, and atmospheric water harvesting. Herein, we report on a dense and uniform MOF-303 membrane fabricated by a facile in situ hydrothermal synthesis approach in the presence of an anodized aluminum oxide (AAO) channel membrane acting as the only Al source and substrate. Interestingly, the MOF-303 isomer can be obtained due to an insufficient amount of organic ligand caused by the less hydrophilic and larger pore size of the AAO substrate. The MOF-based composite membranes possessed surface-charge-governed ionic transport behavior. Moreover, the MOF-303/AAO membrane yielded an output power density of 1.87 W/m2 under a 50-fold KCl concentration gradient. Under a 50-fold gradient of artificial seawater and river water, a maximum power density of 1.46 W/m2 can be obtained. After 30 days of stability testing, the composite membrane still maintained the power output, and the power density was higher than 1.20 W/m2. This work provides a facile and effective strategy for constructing Al-based MOF composite membranes and boosts their applications in harvesting salinity-gradient energy.

Manipulation of Cationic Group Density in Covalent Organic Framework Membranes for Efficient Anion Transport.

Anion exchange membranes with high anion conductivity are highly desired for electrochemical applications. Increasing ion exchange capacity is a straightforward approach to enhancing anion conductivity but faces a challenge in dimensional stability. Herein, we report the design and preparation of three kinds of isoreticular covalent organic framework (COF) membranes bearing tunable quaternary ammonium group densities as anion conductors. Therein, the cationic groups are integrated into the backbones by flexible ether-bonded alkyl side chains. The highly quaternary ammonium-group-functionalized building units endow COF membranes with abundant cationic groups homogeneously distributed in the ordered channels. The flexible side chains alleviate electrostatic repulsion and steric hindrance caused by large cationic groups, ensuring a tight interlayer stacking and multiple interactions. As a result, our COF membranes achieve a high ion exchange capacity and exceptional dimensional stability simultaneously. Furthermore, the effect of the ionic group density on the ion conductivity in rigid COF channels is systematically explored. Experiments and simulations reveal that the ionic group concentration and side chain mobility jointly determine the ion transport behavior, resulting in the abnormal phenomenon that the anion conductivity is not positively correlated to the ionic group density. The optimal COF membrane achieves the ever-reported highest hydroxide ion conductivity over 300 mS cm-1 at 80 °C and 100% RH. This study offers insightful guidelines on the rational design and preparation of high-performance anion conductors.

High‐Strength, Thin PBO Nanofiber Membrane with Long‐Term Stability for Osmotic Energy Conversion

AbstractIon‐selective membrane embedded in a reverse electrodialysis system can achieve the conversion of osmotic energy into electricity. However, the ingenious design and development of pure polymer membranes that simultaneously satisfy excellent mechanical strength, long‐term stability, high power density, and increased testing area is a crucial challenge. Here, high‐strength, thin PBO nanofiber membranes (PBONM) with 3D nanofluidic channels and a thickness of 0.81 µm are prepared via a simple vacuum‐assisted filtration technology. The thin PBONM exhibits excellent mechanical properties: stress of 235.8 MPa and modulus of 16.96 GPa, outperforming the state‐of‐the‐art nanofluidic membranes. The obtained PBONM reveals surface‐charge‐governed ion transport behavior and high ion selectivity of 0.88 at a 50‐fold concentration gradient. The PBO membrane‐based generator delivers a power density of 7.7 and 40.2 W m−2 at 50‐fold and 500‐fold concentration gradient. Importantly, this PBONM presents excellent stability in response to different external environments including various saline solutions, pH, and temperature. In addition, the maximum power density of PBONM reaches up to 5.9 W m−2 under an increased testing area of 0.79 mm2, exceeding other membrane‐based generators with comparable testing areas. This work paves the way for constructing high‐strength fiber nanofluidic membranes for highly efficient osmotic energy conversion.

Composite poly(ethylene oxide)-based solid electrolyte with consecutive and fast ion transport channels constructed by upper-dimensional MIL-53(Al) nanofibers

Novel structural designs for metal organic frameworks (MOFs) are expected to improve ion-transport behavior in composite solid electrolytes. Herein, upper-dimensional MIL-53(Al) nanofibers (MNFs, MIL-53 belongs to the MIL (Material Institute Lavoisier) group) with flower-like nanoflake structures have been designed and constructed via modified hydrothermal coordination. The optimized MNFs with high surface area and porosity can form abundant interfaces with poly(ethylene oxide) (PEO) matrix. The plasticization of MNFs to the PEO matrix will facilitate segmental movement of PEO chains to facilitate Li+ conduction. The unsaturated open metal centers of MNFs can effectively capture bis(trifluoromethanesulfonyl)imide anions (TFSI−) to deliver more free lithium ions for transfer. Moreover, the upper-dimensional nanofiber structure endows lithium ions with a long-range and consecutive transport pathway. The obtained composite solid electrolyte (MNFs@PEO) presents a high ionic conductivity of 4.1 × 10−4 S cm−1 and a great Li+ transference number of 0.4 at 60 °C. The electrolyte also exhibits a stable Li plating/stripping behavior over 1000 h at 0.1 mA cm−1 with inhibited Li dendrite growth. Furthermore, the Li/LiFePO4 and Li/LiNi0.8Mn0.1Co0.1O2 batteries with MNFs@PEO as electrolytes both display great cycling stabilities with high-capacity retention, indicating their potential applications in lithium metal batteries. The study will put forward new inspirations for designing advanced MOF-based composite solid electrolytes.

Ion Transport in Intelligent Nanochannels: A Comparative Analysis of the Role of Electric Field.

This research delves into investigating ion transport behavior within nanochannels, enhanced through modification with a negatively charged polyelectrolyte layer (PEL), aimed at achieving superior control. The study examines two types of electric fields─direct current and alternating current with square, sinusoidal, triangular, and sawtooth waveforms─to understand their impact on ion transport. Furthermore, the study compares symmetric (cylindrical) and asymmetric (conical) nanochannel geometries to assess the influence of overlapping electrical double layers (EDLs) in generating specific electrokinetic behaviors such as ionic current rectification (ICR) and ion selectivity. The research employs the finite element method to solve the coupled Poisson-Nernst-Planck and Navier-Stokes equations under unsteady-state conditions. By considering factors such as electrolyte concentration, soft layer charge density, and electric field type, the study evaluates ion transport performance in charged nanochannels, investigating effects on concentration polarization, electroosmotic flow (EOF), ion current, rectification, and ion selectivity. Notably, the study accounts for ion partitioning between the PEL and electrolyte to simulate real conditions. Findings reveal that conical nanochannels, due to improved EDL overlap, significantly enhance ion transport and related characteristics compared to cylindrical ones. For instance, under ηε = ηD = 0.8, ημ = 2, C0 = 20 mM, and NPEL/NA = 80 mol m-3 conditions, the average EOF for conical and cylindrical geometries is 0.1 and 0.008 m/s, respectively. Additionally, the study explores ion selectivity and rectification based on the electric field type, unveiling the potential of nanochannels as ion gates or diodes. In cylindrical nanochannels, the ICR remains at unity, with lower ion selectivity across waveforms compared to conical channels. Furthermore, rectification and ion selectivity trends are identified as Rf,square > Rf,DC > Rf,triangular > Rf,sinusoidal > Rf,sawtooth and Ssawtooth > Ssinusoidal > Striangular > SDC > Ssquare for conical nanochannels. Our study of ion transport control in nanochannels, guided by tailored electric fields and unique geometries, offers versatile applications in the field of Analytical Chemistry. This includes enhanced sample separation, controlled drug delivery, optimized pharmaceutical analysis, and the development of advanced biosensing technologies for precise chemical analysis and detection. These applications highlight the diverse analytical contributions of our methodology, providing innovative solutions to challenges in chemical analysis and biosensing.

Tracking Ion Transport in Nanochannels via Transient Single‐Particle Imaging

AbstractThe transport behavior of ions in the nanopores has an important impact on the performance of the electrochemical devices. Although the classical Transmission‐Line (TL) model has long been used to describe ion transport in pores, the boundary conditions for the applicability of the TL model remain controversial. Here, we investigated the transport kinetics of different ions, within nanochannels of different lengths, by using transient single‐particle imaging with temporal resolution up to microseconds. We found that the ion transport kinetics within short nanochannels may deviate significantly from the TL model. The reason is that the ion transport under nanoconfinement is composed of multi basic stages, and the kinetics differ much under different stage domination. With the shortening of nanochannels, the electrical double layer (EDL) formation would become the “rate‐determining step” and dominate the apparent ion kinetics. Our results imply that using the TL model directly and treating the in‐pore mobility as an unchanged parameter to estimate the ion transport kinetics in short nanopores/nanochannels may lead to orders of magnitude bias. These findings may advance the understanding of the nanoconfined ion transport and promote the related applications.

Tracking Ion Transport in Nanochannels via Transient Single-Particle Imaging.

The transport behavior of ions in the nanopores has an important impact on the performance of the electrochemical devices. Although the classical Transmission-Line (TL) model has long been used to describe ion transport in pores, the boundary conditions for the applicability of the TL model remain controversial. Here, we investigated the transport kinetics of different ions, within nanochannels of different lengths, by using transient single-particle imaging with temporal resolution up to microseconds. We found that the ion transport kinetics within short nanochannels may deviate significantly from the TL model. The reason is that the ion transport under nanoconfinement is composed of multi basic stages, and the kinetics differ much under different stage domination. With the shortening of nanochannels, the electrical double layer (EDL) formation would become the "rate-determining step" and dominate the apparent ion kinetics. Our results imply that using the TL model directly and treating the in-pore mobility as an unchanged parameter to estimate the ion transport kinetics in short nanopores/nanochannels may lead to orders of magnitude bias. These findings may advance the understanding of the nanoconfined ion transport and promote the related applications.

Covalently Functionalized Nanopores for Highly Selective Separation of Monovalent Ions.

Biological ion channels possess prominent ion transport performances attributed to their critical chemical groups across the continuous nanoscale filters. However, it is still a challenge to imitate these sophisticated performances in artificial nanoscale systems. Herein, this work develops the strategy to fabricate functionalized graphene nanopores in pioneer based on the synergistic regulation of the pore size and chemical properties of atomically thin confined structure through decoupling etching combined with in situ covalent modification. The modified graphene nanopores possess asymmetric ion transport behaviors and efficient monovalent metal ions sieving (K+ /Li+ selectivity ≈48.6). Meanwhile, it also allows preferential transport for cations, the resulting membranes exhibit a K+ /Cl- selectivity of 76 and a H+ /Cl- selectivity of 59.3. The synergistic effects of steric hindrance and electrostatic interactions imposing a higher energy barrier for Cl- or Li+ across nanopores lead to ultra-selective H+ or K+ transport. Further, the functionalized graphene nanopores generate a power density of 25.3W m-2 and a conversion efficiency of 33.9%, showing potential application prospects in energy conversion. The theoretical studies quantitatively match well with the experimental results. The feasible preparation of functionalized graphene nanopores paves the way toward direct investigation on ion transport mechanism and advanced design in devices.

Molecular dynamic study on the transport properties of ionic liquids in ZTC porous carbon materials

The adsorption and diffusion behavior of ions within electrodes have a significant impact on the energy density and charging/discharging speed of supercapacitors. Zeolite-Templated Carbon (ZTC) material, a type of porous carbon material characterized by well-defined pore shape and spatial structure, is recognized as a promising electrode material owing to its numerous advantages. This study employs molecular dynamics simulations to investigate the diffusion and adsorption profiles of ionic liquids [EMI][BF4] in different types of ZTC materials as electrodes. Additionally, the effect of ion size, pore dimension, pore shape, and the properties of the adsorbed ions are discussed. The degree of confinement (DOC) and ion diffusivity are thoroughly analyzed to elucidate the transport behavior of ions within the ZTC pores. The results demonstrate that the diffusion coefficient and degree of confinement of ionic liquids predominantly depend on the anion size and the pore size of the porous carbon. Surprisingly, in certain cases, larger anions exhibit enhanced diffusion ability and adsorption effect. These findings unravel the underlying transport mechanism of ions in ZTC materials and provide valuable theoretical insights for the application of ZTC materials as electrodes in the field of supercapacitors.

Boosted Charge-Transfer behavior for ultrafast Zn storage by constructing intrinsic heterojunction of ammonium vanadate nanoribbons coupling with interlaminar MXenes nanosheets

Ammonium vanadate (NH4V4O10, NHVO) is one of the most promising cathode materials for aqueous zinc-ion batteries (ZIBs) owing to its inherent large interplanar spacing, highly reversible electrochemical reaction mechanism and admirable specific capacity. However, the fragile interlayer structure and sluggish electron transport behavior generally cause tardy electrochemical reaction kinetics and result in poor cycling stability and rate capabilities. In this work, a novel intrinsic heterojunction cathode (NHVO@MX) of NHVO nanoribbons coupling with inserted Mxenes (MX) nanosheets is rationally constructed on a flexible carbon cloth substrate for wearable ZIB applications. The intercalated MX nanosheets not only serve as the spacer to isolate the NHVO interlayers as well as efficiently accelerate electron and ion transport behaviors, hence preserving the numerous exposed active areas required for rich and rapid Zn storage. Most impressively, it presents the lowest charge-transfer barrier among all the reported vanadate-based materials induced by the interlaminar MX nanosheets, demonstrated by both experimental measurement and theoretical calculation. As a result, the as-prepared heterojunction cathode delivers high specific capacity of 437 mAh·g−1, excellent rate capability and ultralong cycling life (over 2000 cycles). Therefore, manufacturing the heterojunction laminar cathode with incorporated MX can be considered a prospective strategy for next-generation advanced ZIBs.