Zinc-Ion Anchor Induced Highly Reversible Zn Anodes for High Performance Zn-Ion Batteries.

Unstable Zn interface with serious detrimental parasitic side-reactions and uncontrollable Zn dendrites severely plagues the practical application of aqueous zinc-ion batteries. The interface stability was closely related to the electrolyte configuration and Zn2+ depositional behavior. In this work, a unique Zn-ion anchoring strategy is originally proposed to manipulate the coordination structure of solvated Zn-ions and guide the Zn-ion depositional behavior. Specifically, the amphoteric charged ion additives (denoted as DM), which act as zinc-ion anchors, can tightly absorb on the Zn surface to guide the uniform zinc-ion distribution by using its positively charged -NR4 + groups. While the negatively charged -SO3 - groups of DM on the other hand, reduces the active water molecules within solvation sheaths of Zn-ions. Benefiting from the special synergistic effect, Zn metal exhibits highly ordered and compact (002) Zn deposition and negligible side-reactions. As a result, the advanced Zn||Zn symmetric cell delivers extraordinarily 7000 hours long lifespan (0.25 mA cm-2, 0.25 mAh cm-2). Additionally, based on this strategy, the NH4V4O10||Zn pouch-cell with low negative/positive capacity ratio (N/P ratio=2.98) maintains 80.4 % capacity retention for 180 cycles. A more practical 4 cm*4 cm sized pouch-cell could be steadily cycled in a high output capacity of 37.0 mAh over 50 cycles.

Intrinsically Decoupled Coordination Chemistries Enable Quasi-Eutectic Electrolytes with Fast Kinetics toward Enhanced Zinc-Ion Capacitors.

Eutectic electrolytes show potential beyond conventional low-concentration electrolytes (LCEs) in zinc (Zn)-ion capacitors (ZICs) yet suffer from high viscosity and sluggish kinetics. Herein, we originally develop an intrinsically decoupling strategy to address these issues, producing a novel electrolyte termed "quasi-eutectic" electrolyte (quasi-EE). Joint experimental and theoretical analyses confirm its unique solution coordination structure doped with near-LCE domains. This enables the quasi-EE well inherit the advanced properties at deep-eutectic states while provide facilitated kinetics as well as lower energy barriers via a vehicle/hopping-hybridized charge transfer mechanism. Consequently, a homogeneous electroplating pattern with much enhanced Sandꞌs time is achieved on the Zn surface, followed by a twofold prolonged service-life with drastically reduced concentration polarization. More encouragingly, the quasi-EE also delivers increased capacitance output in ZICs, which is elevated by 12.4%-144.6% compared to that before decoupling. Furthermore, the pouch cell with a cathodic mass loading of 36.6 mg cm-2 maintains competitive cycling performances over 600 cycles, far exceeding other Zn-based counterparts. This work offers fresh insights into eutectic decoupling and beyond.

Chelating Additive Regulating Zn-Ion Solvation Chemistry for Highly Efficient Aqueous Zinc-Metal Battery.

Aqueous zinc-metal batteries (AZMBs) usually suffered from poor reversibility and limited lifespan because of serious water induced side-reactions, hydrogen evolution reactions (HER) and rampant zinc (Zn) dendrite growth. Reducing the content of water molecules within Zn-ion solvation sheaths can effectively suppress those inherent defects of AZMBs. In this work, we originally discovered that the two carbonyl groups of N-Acetyl-ϵ-caprolactam (N-ac) chelating ligand can serve as dual solvation sites to coordinate with Zn2+, thereby minimizing water molecules within Zn-ion solvation sheaths, and greatly inhibit water-induced side-reactions and HER. Moreover, the N-ac chelating additive can form a unique physical barrier interface on Zn surface, preventing the harmful contacting with water. In addition, the preferential adsorption of N-ac on Zn (002) facets can promote highly reversible and dendrite-free Zn2+ deposition. As a result, Zn//Cu half-cell within N-ac added electrolyte delivered ultra-high 99.89 % Coulombic efficiency during 8000 cycles. Zn//Zn symmetric cells also demonstrated unprecedented long life of more than 9800 hours (over one year). Aqueous Zn//ZnV6O16 ⋅ 8H2O (Zn//ZVO) full-cell preserved 78 % capacity even after ultra-long 2000 cycles. A more practical pouch-cell was also obtained (90.2 % capacity after 100 cycles). This method offers a promising strategy for accelerating the development of highly efficient AZMBs.

Lithiophilic Magnetic Host Facilitates Target-Deposited Lithium for Practical Lithium-Metal Batteries.

Lithium-metal shows promising prospects in constructing various high-energy-density lithium-metal batteries (LMBs) while long-lasting tricky issues including the uncontrolled dendritic lithium growth and infinite lithium volume expansion seriously impede the application of LMBs. In this work, it is originally found that a unique lithiophilic magnetic host matrix (Co3 O4 -CCNFs) can simultaneously eliminate the uncontrolled dendritic lithium growth and huge lithium volume expansion that commonly occur in typical LMBs. The magnetic Co3 O4 nanocrystals which inherently embed on the host matrix act as nucleation sites and can also induce micromagnetic field and facilitate a targeted and ordered lithium deposition behavior thus, eliminating the formation of dendritic Li. Meanwhile, the conductive host can effectively homogenize the current distribution and Li-ion flux, thus, further relieving the volume expansion during cycling. Benefiting from this, the featured electrodes demonstrate ultra-high coulombic efficiency of 99.1% under 1 mA cm-2 and 1 mAh cm-2 . Symmetric cell under limited Li (10 mAh cm-2 ) inspiringly delivers ultralong cycle life of 1600 h (under 2 mA cm-2 , 1 mAh cm-2 ). Moreover, LiFePO4 ||Co3 O4 -CCNFs@Li full-cell under practical condition of limited negative/positive capacity ratio (2.3:1) can deliver remarkably improved cycling stability (with 86.6% capacity retention over 440 cycles).

Aligned Dipoles Induced Electric-Field Promoting Zinc-Ion De-Solvation toward Highly Stable Dendrite-Free Zinc-Metal Batteries.

Water-induced parasitic reactions and uncontrolled dendritic Zn growth are long-lasting tricky problems that severely hinder the development of aqueous zinc-metal batteries. Those notorious issues are closely related to electrolyte configuration and zinc-ion transport behavior. Herein, through constructing aligned dipoles induced electric-field on Zn surface, both the solvation structure and transport behavior of zinc-ions are fundamentally changed. The vertically ordered zinc-ion migration trajectory and gradually concentrated zinc-ion achieved inside the polarized electric-field remarkably eliminate water related side-reactions and Zn dendrites. Zn-metal under the polarized electric-field demonstrated significantly improve reversibility and a dendrite-free surface with strong (002) Zn deposition texturing. Zn||Zn symmetric cell delivers greatly prolonged lifespan up to 1400 h (17 times longer than that of the cell based on bare Zn) while the Zn||Cu half-cell demonstrate ultrahigh 99.9% coulombic efficiency. NH4 V4 O10 ||Zn half-cell delivered exceptional-high 132 mAh g-1 capacity after ultralong 2000 cycles (≈100% capacity retention). In addition, MnO2 ||Zn pouch-cell under aligned dipoles induced electric-field maintains 87.9% capacity retention after 150 cycles under practical condition of high MnO2 mass loading (≈10 mg cm-2 ) and limited N/P ratio. It is considered that this new strategy can also be implemented to other metallic batteries and spur the development of batteries with long-lifespan and high-energy-density.

Multichannel Ca2+ Generator for Synergistic Tumor Therapy via Intracellular Ca2+ Overload and Chemotherapy.

Ca2+ overload has attracted an increasing attention due to its benefit of precise cancer therapy, but its efficacy is limited by the strong Ca2+ excretion of cancer cells. Moreover, monotherapy of Ca2+ overload usually fails to treat tumors satisfactorily. Herein, we develop a multifunctional nanosystem that could induce Ca2+ overload by multipathway and simultaneously produce chemotherapy for synergistic tumor therapy. The nanosystem (CaMSN@CUR) is prepared by synthesizing a Ca-doped mesoporous silica nanoparticle (CaMSN) followed by loading the anticancer drug curcumin (CUR). CaMSN serves as the basis Ca2+ generator to induce Ca2+ overload directly in the intracellular environment by acid-triggered Ca2+ release, while CUR could not only exhibit chemotherapy but also facilitate Ca2+ release from the endoplasmic reticulum to the cytoplasm and inhibit Ca2+ efflux out of cells to further enhance Ca2+ overload. The in vitro and in vivo results show that CaMSN@CUR could exhibit a remarkable cytotoxicity against 4T1 cells and significantly inhibit tumor growth in 4T1 tumor-bearing mice via the synergy of Ca2+ overload and CUR-mediated chemotherapy. It is expected that the designed CaMSN@CUR has a great potential for effective tumor therapy.

In Situ Defect Induction in Close-Packed Lattice Plane for the Efficient Zinc Ion Storage.

In situ electrochemical activation brings unexpected electrochemical performance improvements to electrode materials, but the mechanism behind it still needs further study. Herein, an electrochemically in situ defect induction in close-packed lattice plane of vanadium nitride oxide (VNx Oy ) in aqueous zinc-ion battery is reported. It is verified by theoretical calculation and experiment that the original compact structure is not suitable for the insert of Zn2+ ion, while a highly active one after the initial electrochemical activization accompanied by the in situ defect induction in close-packed lattice plane of VNx Oy exhibits efficient zinc ion storage. As expected, activated VNx Oy can achieve very high reversible capacity of 231.4 mA h g-1 at 1 A g-1 and cycle stability upto 6000 cycles at 10 A g-1 with a capacity retention of 94.3%. This work proposes a new insight for understanding the electrochemically in situ transformation to obtain highly active cathode materials for the aqueous zinc-ion batteries.

Serpentine Ni3 Ge2 O5 (OH)4 Nanosheets with Tailored Layers and Size for Efficient Oxygen Evolution Reactions.

Layered serpentine Ni3 Ge2 O5 (OH)4 is compositionally active and structurally favorable for adsorption and diffusion of reactants in oxygen evolution reactions (OER). However, one of the major problems for these materials is limited active sites and low efficiency for OER. In this regard, a new catalyst consisting of layered serpentine Ni3 Ge2 O5 (OH)4 nanosheets is introduced via a controlled one-step synthetic process where the morphology, size, and layers are well tailored. The theoretical calculations indicate that decreased layers and increased exposure of (100) facets in serpentine Ni3 Ge2 O5 (OH)4 lead to much lower Gibbs free energy in adsorption of reactive intermediates. Experimentally, it is found that the reduction in number of layers with minimized particle size exhibits plenty of highly surface-active sites of (100) facets and demonstrates a much enhanced performance in OER than the corresponding multilayered nanosheets. Such a strategy of tailoring active sites of serpentine Ni3 Ge2 O5 (OH)4 nanosheets offers an effective method to design highly efficient electrocatalysts.

Topical Application of Keratinocyte Growth Factor Conjugated Gold Nanoparticles Accelerate Wound Healing.

Keratinocyte growth factor (KGF) has been demonstrated to specifically stimulate the multiplication and migration of keratinocytes. However, due to rapid degradation, the results of topical application of growth factors on wounds are unsatisfactory. In this study, we cross-linked KGF to the surface of gold nanoparticles (GNPs) and explored their effects on wound healing. The as-synthesized nanocomposite (KGF-GNPs) displayed good colloidal stability, decent biocompatibility as well as negligible cellular cytotoxicity. The in vitro cellular experimental results demonstrated that KGF-GNPs could effectively promote the proliferation of keratinocytes in contrast to bare GNPs or KGF. Furthermore, in animal full-thickness wound model, KGF-GNPs are more conducive to wound healing than bare GNPs or KGF. KGF-GNPs enhanced wound healing by promoting wound re-epithelialization rather than granulation. The superior biocompatibility, colloidal depressiveness and biological activity of this nanocomposite indicate that it could be utilized as a promising wound healing drug for clinical application in the future.

Nb2O5 microstructures: a high-performance anode for lithium ion batteries.

We report the synthesis of three-dimensional (3D) urchin-like Nb2O5 microstructures by a facile hydrothermal approach with subsequent annealing treatment. As anode materials for lithium-ion batteries, the 3D urchin-like Nb2O5 microstructures exhibit superior electrochemical performance with excellent rate capability as well as long-term cycling stability. The electrode delivers high capacity of 131 mA h g-1 after 1000 cycles at a high current density of 1 A g-1. The excellent electrochemical performance suggests the 3D urchin-like Nb2O5 microstructures may be a promising anode candidate for high-power lithium ion batteries.

Template-free synthesis of highly porous V2O5 cuboids with enhanced performance for lithium ion batteries.

Highly porous hierarchical V2O5 cuboids have been synthesized by a template-free PVP-assisted polyxol method and the formation mechanism is studied. The cuboids are assembled from numerous mesoporous nanoplates and the preferred orientation of each single nanoplate exposes the 〈110〉 facets, facilitating lithium-ion diffusion by offering a prior channel. This material exhibits a high capacity of 143 mA h g(-1), high rate capacity of 10 C and long life cycling performance up to 1000 cycles. The excellent electrochemical performance of V2O5 cuboid electrodes is due to its unique porous cuboid morphology and optimized structural stability upon cycling. This research provides an effective route to the construction of complex porous architectures assembled from nanocrystals through a surfactant-assisted synthesis method.

Solid-State Electrolytes and Electrode/Electrolyte Interfaces in Rechargeable Batteries.

Solid-state batteries (SSBs) are considered to be one of the most promising candidates for next-generation energy storage systems due to the high safety, high energy density and wide operating temperature range of solid-state electrolytes (SSEs) they use. Unfortunately, the practical application of SSEs has rarely been successful, which is largely attributed to the low chemical stability and ionic conductivity, ineluctable solid-solid interface issues including limited ion transport channels, high energy barriers, and poor interface contact. A comprehensive understanding of ion transport mechanisms of various SSEs, interactions between fillers and polymer matrixes and the role of the interface in SSBs are indispensable for rational design and performance optimization of novel electrolytes. The categories, research advances and ion transport mechanism of inorganic glass/ceramic electrolytes, polymer-based electrolytes and corresponding composite electrolytes are detailly summarized and discussed. Moreover, interface contact and compatibility between electrolyte and cathode/anode are also briefly discussed. Furthermore, the electrochemical characterization methods of SSEs used in different types of SSBs are also introduced. On this basis, the principles and prospects of novel SSEs and interface design are curtly proposed according to the development requirements of SSBs. Moreover, the advanced characterizations for real-time monitoring of interface changes are also brought forward to promote the development of SSBs.

Unleashing the high energy potential of zinc-iodide batteries: high-loaded thick electrodes designed with zinc iodide as the cathode.

The realization of high energy is of great importance to unlock the practical potential of zinc-iodine batteries. However, significant challenges, such as low iodine loading (mostly less than 50 wt%), restricted iodine reutilization, and severe structural pulverization during cycling, compromise its intrinsic features. This study introduces an optimized, fully zincified zinc iodide loaded onto a hierarchical carbon scaffold with high active component loading and content (82 wt%) to prepare a thick cathode for enabling high-energy Zn-I2 batteries. The synergistic interactions between nitrogen heteroatoms and cobalt nanocrystals within the porous matrix not only provide forceful chemisorption to lock polyiodide intermediates but also invoke the electrocatalytic effects to manipulate efficient iodine conversion. The ZnI2 cathode could effectively alleviate continuous volumetric expansion and maximize the utilization of active species. The electrochemical examinations confirm the thickness-independent battery performance of assembled Zn-I2 cells due to the ensemble effect of composite electrodes. Accordingly, with a thickness of 300 µm and ZnI2 loading of up to 20.5 mg cm-2, the cathode delivers a specific capacity of 92 mA h gcathode-1 after 2000 cycles at 1C. Moreover, the Zn-I2 pouch cell with ZnI2 cathode has an energy density of 145 W h kgcathode-1 as well as a stable long cycle life.

Water Catchers within Sub-Nano Channels Promote Step-by-Step Zinc-Ion Dehydration Enable Highly Efficient Aqueous Zinc-Metal Batteries.

Zinc metal suffers from violent and long-lasting water-induced side reactions and uncontrollable dendritic Zn growth, which seriously reduce the coulombic efficiency (CE) and lifespan of aqueous zinc-metal batteries (AZMBs). To suppress the corresponding harmful effects of the highly active water, a stable zirconium-based metal-organic framework with water catchers decorated inside its sub-nano channels is used to protect Zn-metal. Water catchers within narrow channels can constantly trap water molecules from the solvated Zn-ions and facilitate step-by-step desolvation/dehydration, thereby promoting the formation of an aggregative electrolyte configuration, which consequently eliminates water-induced corrosion and side reactions. More importantly, the functionalized sub-nano channels also act as ion rectifiers and promote fast but even Zn-ions transport, thereby leading to a dendrite-free Zn metal. As a result, the protected Zn metal demonstrates an unprecedented cycling stability of more than 10 000 h and an ultra-high average CE of 99.92% during 4000 cycles. More inspiringly, a practical NH4V4O10//Zn pouch-cell is fabricated and delivers a capacity of 98 mAh (under high cathode mass loading of 25.7 mg cm-2) and preserves 86.2% capacity retention after 150 cycles. This new strategy in promoting highly reversible Zn metal anodes would spur the practical utilization of AZMBs.

Template-free synthesis of hierarchical vanadium-glycolate hollow microspheres and their conversion to V2O5 with improved lithium storage capability.

Nanosheet-assembled hierarchical V(2)O(5) hollow microspheres are successfully obtained from V-glycolate precursor hollow microspheres, which in turn are synthesized by a simple template-free solvothermal method. The structural evolution of the V-glycolate hollow microspheres has been studied and explained by the inside-out Ostwald-ripening mechanism. The surface morphologies of the hollow microspheres can be controlled by varying the mixture solution and the solvothermal reaction time. After calcination in air, hierarchical V(2)O(5) hollow microspheres with a high surface area of 70 m(2) g(-1) can be obtained and the structure is well preserved. When evaluated as cathode materials for lithium-ion batteries, the as-prepared hierarchical V(2)O(5) hollow spheres deliver a specific discharge capacity of 144 mA h g(-1) at a current density of 100 mA g(-1), which is very close to the theoretical capacity (147 mA h g(-1)) for one Li(+) insertion per V(2)O(5) . In addition, excellent rate capability and cycling stability are observed, suggesting their promising use in lithium-ion batteries.

Fabrication of the micro/nano-structure superhydrophobic surface on aluminum alloy by sulfuric acid anodizing and polypropylene coating.

The preparation of the superhydrophobic surface on aluminum alloy by anodizing and polypropylene (PP) coating was reported. Both the different anodizing process and different PP coatings of aluminum alloy were investigated. The effects of different anodizing conditions, such as electrolyte concentration, anodization time and current on the superhydrophobic surface were discussed. By PP coating after anodizing, a good superhydrophobic surface was facilely fabricated. The optimum conditions for anodizing were determined by orthogonal experiments. After the aluminium-alloy was grinded with 600# sandpaper, pretreated by 73 g/L hydrochloric acid solution at 1 min, when the concentration of sulfuric acid was 180 g/L, the concentration of oxalic acid was 5 g/L, the concentration of potassium dichromate was 10 g/L, the concentration of chloride sodium was 50 g/L and 63 g/L of glycerol, anodization time was 20 min, and anodization current was 1.2 A/dm2, anodization temperature was 30-35 degrees C, the best micro-nanostructure aluminum alloy films was obtained. On the other hand, the PP with different concentrations was used to the PP with different concentrations was used to coat the aluminum alloy surface after anodizing. The results showed that the best superhydrophobicity was achieved by coating PP, and the duration of the superhydrophobic surface was improved by modifying the coat the aluminum alloy surface after anodizing. The results showed that the best superhydrophobicity was surface with high concentration PP. The morphologies of micro/nano-structure superhydrophobic surface were further confirmed by scanning electron microscope (SEM). The material of PP with the low surface free energy combined with the micro/nano-structures of the surface resulted in the superhydrophobicity of the aluminum alloy surface.

Preparation of micro/nano-structure superhydrophobic film on aluminum plates using galvanic corrosion method.

A simple and novel approach has been developed to obtain a microporous film with compound nanoparticles on the surface of aluminum alloy substrate using the galvanic corrosion method. The wettability of the surface changes from hydrophilicity to superhydrophobicity after chemical modification with stearic acid (SA). The water contact angle (WCA) and sliding angle (WSA) of superhydrophobic aluminum alloy surface (SAAS) are 154 degrees and 9 degrees, respectively. The roughness of the aluminum substrate increases after the oxidation reaction. The porous aluminum matrix surface is covered with irregularly shaped holes with a mean radius of about 15 microm, similar to the surface papillae of natural Lotus leaf, with villus-like nanoparticles array on pore surfaces. The superhydrophobic property is attributed to this special surface morphology and low surface energy SA. X-ray powder diffraction (XRD) pattern and Energy Dispersive X-Ray Spectroscopy (EDS) spectrum indicate that Al2O3, Al(OH)3 and AIO(OH) has been formed on the surface of aluminum substrate after the oxidation reaction. The Raman spectra indicate that C-H bond from SA and the Al-O are formed on the SAAS. The as-formed SAAS has good stability.

Enzyme-Triggered Size-Switchable Nanosystem for Deep Tumor Penetration and Hydrogen Therapy.

The poor penetration of nanocarriers within tumor dense extracellular matrices (ECM) greatly restricts the access of anticancer drugs to the deep tumor cells, resulting in low therapeutic efficacy. Moreover, the high toxicity of the traditional chemotherapeutics inevitably causes undesirable side effects. Herein, taking the advantages of biosafe H2 and small-sized nanoparticles in diffusion within tumor ECM, we develop a matrix metalloprotease 2 (MMP-2) responsive size-switchable nanoparticle (UAMSN@Gel-PEG) that is composed of ultrasmall amino-modified mesoporous silica nanoparticles (UAMSN) wrapped within a PEG-conjugated gelatin to deliver H2 to the deep part of tumors for effective gas therapy. Ammonia borane (AB) is chosen as the H2 prodrug that can be effectively loaded into UAMSN by hydrogen-bonding adsorption. Gelatin is used as the substrate of MMP-2 to trigger size change and block AB inside UAMSN during blood circulation. PEG is introduced to further increase the particle size and endow the nanoparticle with long blood circulation to achieve effective tumor accumulation via the EPR effect. After accumulation into the tumor site, MMP-2 promptly digests gelatin to expose UAMSN loading AB for deep tumor penetration. Upon stimulation by the acidic tumor microenvironment, AB decomposes into H2 for further intratumor diffusion to achieve effective hydrogen therapy. Consequently, such a simultaneous deep tumor penetration of nanocarriers and H2 results in an evident suppression on tumor growth in a 4T1 tumor-bearing model without any obvious toxicity on normal tissues. Our synthetic nanosystem provides a promising strategy for the development of nanomedicines with enhanced tumor permeability and good biosafety for efficient tumor treatment.

Unique ion rectifier intermediate enabled by ultrathin vermiculite sheets for high-performance Zn metal anodes.

Metallic Zn represents as a primary choice in fabricating various aqueous Zn-ion batteries (ZIBs), however challenging issues including dendrite growth and parasitic reactions at the anode/electrolyte interface, considerably hamper its practical implementation in large-scale energy storage. Herein, we report a low-cost multifunctional ion rectifier (IRT) as an artificial intermediate to reform Zn anode, which can practically eliminate the above issues. The hydrophobic shell (polyvinylidene difluoride) can suppress Zn interfacial corrosion with an inhibition efficiency of 94.8% by repelling water molecules from the bulk electrolyte. Additionally, negatively-charged ion channels inside the zincophilic core (ultrathin vermiculite sheets) induce de-solvating redistribution effect on Zn2+ ions flux, enabling a high ions transference number (0.79) for dendrite-free Zn deposition. This leads to exceptional Zn/Zn2+ reversibility in metallic Zn with IRT stabilization. The remarkable Coulombic efficiency (99.8%, 2000 cycles) for asymmetrical batteries, and a long lifespan (1600 h) with ultrahigh cumulative capacity of 2400 mAh cm-2 for symmetrical batteries, are successfully achieved. More encouragingly, the Zn//NH4V4O10 pouch cell retains 94.3% of its original capacity after 150 cycles at 1 A g-1. We believe that this low-cost and high-efficiency tactic could pave a promising path for anode surface modification.

Highly Stable Aqueous Zinc Metal Batteries Enabled by an Ultrathin Crack-Free Hydrophobic Layer with Rigid Sub-Nanochannels.

Aqueous zinc-metal batteries (AZMBs) have received tremendous attentions due to their high safety, low cost, environmental friendliness, and simple process. However, zinc-metal still suffer from uncontrollable dendrite growth and surface parasitic reactions that reduce the Coulombic efficiency (CE) and lifetime of AZMBs. These problems which are closely related to the active water are not well-solved. Here, an ultrathin crack-free metal-organic framework (ZIF-7x -8) with rigid sub-nanopore (0.3 nm) is constructed on Zn-metal to promote the de-solvation of zinc-ions before approaching Zn-metal surface, reduce the contacting opportunity between water and Zn, and consequently eliminate water-induced corrosion and side-reactions. Due to the presence of rigid and ordered sub-nanochannels, Zn-ions deposits on Zn-metal follow a highly ordered manner, resulting in a dendrite-free Zn-metal with negligible by-products, which significantly improve the reversibility and lifespan of Zn-metals. As a result, Zn-metal protected by ultrathin crack-free ZIF-7x -8 layer exhibits excellent cycling stability (over 2200 h) and extremely-high 99.96% CE during 6000 cycles. The aqueous PANI-V2 O5 //ZIF-7x -8@Zn full-cell preserves 86% high-capacity retention even after ultra-long 2000 cycles. The practical pouch-cell can also be cycled for more than 120 cycles. It is believed that the simple strategy demonstrated in this work can accelerate the practical utilizations of AZMBs.