Zn Deposits Research Articles

Superhydrophobic metal-organic framework layers as multifunctional ion-conducting interfaces for ultra-stable Zn anodes

Aqueous zinc batteries (AZBs) show great promise for cost-effective, high-safety, and large-scale energy storage. Yet, corrosion and dendrite formation at the Zn anode interface undermine its stability, shortening the cycle life. In this work, a fluorosilane-modified metal-organic framework layer (F-MOF) is successfully prepared as a multifunctional ion-conductive interface to stabilize the Zn anode. The designed MOF-based artificial layer provides a uniform pathway for Zn deposition, while its hydrophobic nature prevents negative effects such as hydrogen evolution and corrosion. According to density functional theory (DFT) calculations, the hydration energy of Zn2+ in F-MOF@Zn(002) is reduced while the adsorption energy for Zn2+ is increased. This facilitates the desolvation process on the Zn anode surface, promoting uniform Zn deposition. Consequently, the lifespan of the F-MOF-coated Zn anode extends beyond 2000 h at a current density of 1 mA cm−2 (areal capacity: 0.5 mAh cm−2), significantly outlasting both bare Zn (225 h) and MOF-coated Zn (751 h) anodes. Additionally, the assembled coin cells and pouch-type full cells prove the practical availability of F-MOF@Zn anodes for AZBs. The F-MOF@Zn//MnO2 full cell maintains a high-capacity retention exceeding 91.9 % even after 1000 cycles. This work highlights the practical application potential of hydrophobic MOF coatings for AZBs.

Polyoxometalate Initiated In situ Conformal Coating of Multifunctional Hybrid Artificial Layers for High Performance Zinc Metal Anodes

AbstractAqueous zinc (Zn) metal batteries are very attractive owing to the high theoretical capacity (820 mAh g−1), meritable electrode potential (−0.76 V vs SHE), low cost, and environmental friendliness of Zn metal anodes. However, the dendrite formation, corrosion, and water decomposition on Zn metal anodes should be resolved for their practical applications. Herein, conformally coated multifunctional organic/inorganic hybrid artificial layers are demonstrated for the reversible and stable Zn deposition. These hybrid layers are synthesized through polyoxometalate (POM) initiated polymerization into poly(1,3‐dioxolane) (Poly(DOL)) and directly coated onto the Zn surface. Moreover, POM acted as chemical bridge connecting Poly(DOL) with Zn metal anode to construct mechanically robust layers with a thickness of ≈40 nm. The fast and selective Zn2+ ion transport of multifunctional POM/Poly(DOL) hybrid layer (POMDOL) and their preferential growth into (002) crystalline plane are attributed to the reversible Zn deposition. Accordingly, POMDOL coated Zn (PDOLZn) anodes achieves an extended cycling period up to 2,876 hours with a cumulative capacity of 29 Ah g−1 at 20 mA cm−2 and 1 mAh cm−2. Moreover, depth of discharge (DOD) of 40% is achieved. Consequently, the PDOLZn || β‐MnO2 full cells delivered the high specific capacity of 245 mAh g−1 and long‐term stability over 1 000 cycles.

Low-cost deposition of tunable band gap Zn(O,S) as electron transport layer for crystalline silicon heterojunction solar cells

In recent years, the research on silicon heterojunction (HJT) solar cells based on dopant-free contacts has experienced rapid development. Zn(O,S) is a low work function n-type semiconductor compound with tunable band gap that can be used as the electron transport layer (ETL) in HJT solar cells. In our work, we choose Zn(O,S) as ETL and deposit it via the low-cost chemical bath deposition (CBD) method. Uniform and fast growth of Zn(O,S) films can be obtained by regulating the concentration of the complexing agent and the ratio of reactants to reduce the generation of impurities. To further achieve band matching with c-Si, the Zn(O,S) films are processed with air-annealing to modify the elemental ratios. The air-annealing lowers the interfacial electron transport barrier, which promotes charge separation and transport, thus reducing carrier recombination at the interface. Finally, the PCE of HJT solar cell based on CBD-Zn(O,S) ETL is close to 15 %, providing a new potential route for the development of low-cost HJT solar cells.

Electrodeposited Zn-Mn on three-dimensional electrodes as anodes in liquid and quasi-solid-state zinc-air batteries

Zinc-air batteries (ZABs) are eco-friendly and sustainable energy storage devices. There are different challenges to overcome in ZABs, where anodic issues such as shape changes, passivation, self-corrosion, and dendrite formation require urgent solutions. In this work, Zn and Zn-Mn alloys were electrodeposited on three-dimensional porous carbon electrodes varying the Mn composition (2, 20 and 40 g L−1) and studying its effect during the operation of a 6 M KOH liquid ZAB and a quasi-solid-state ZAB based on poly(vinyl alcohol)/poly(acrylic acid) PVA/PAA gel polymer electrolyte (GPE). Scanning electron microscopy (SEM) images indicated that Zn and Zn-Mn were deposited as platelet-like bi-dimensional structures. Additionally, the use of 20 and 40 g L−1 of the Mn precursor resulted in larger Zn deposition covering the 3D structure of the carbon paper. Elemental analysis indicated that the Mn content in Zn-Mn was 1.3, 2.4 and 6 %. In the aqueous ZAB, the Zn-Mn with 2.4 % Mn enabled to increase the maximum current density achieving the highest power density of 45 mW cm⁻2. In QSS-ZAB, Zn-Mn at 1.3 and 2.4. % Mn displayed higher stability to recovery after demanding different current densities, while the first anode displayed higher cyclability, presenting a similar round trip after 240 charge/discharge cycles This ZAB was maintained functional during 290 cycles vs. 120 cycles for Zn foil. The rechargeability was improved because of the decrease in Zn dendritic growth and passivation.

Hydrophilic and Insulative Interface Strategy Against Side Reactions for Dendrite‐Free Zinc Metal Anodes

AbstractThe zinc dendrite growth and the parasitic hydrogen evolution reactions (HER) hinder the commercialization of zinc batteries. To address this, a hydroxyl‐rich Boehmite coating (HR‐BC) strategy is developed that combines excellent electrical insulation and high zinc ion conductivity. The hydrophilic hydroxyl groups facilitate hydrogen bond formation with the hydrated zinc ions, accelerating the de‐solvation process and suppressing the HER. Additionally, the electrically insulative nature of Boehmite prevents the reduction of zinc ions within HR‐BC and results in preferential Zn deposition underneath it, leading to a dendrite‐free “sandwich structure” of HR‐BC//Zn deposition//Zn foil. Symmetric cells using HR‐BC‐Zn electrodes obtain an ultralong and stable cycling lifetime of 1700 h at 5 mA cm−2, along with a high cumulative plating capacity of 4250 mAh cm−2. When paired with a V2O5 cathode, the HR‐BC‐Zn anode demonstrates a high capacitance retention of 90% and an average Coulombic efficiency (CE) of 99.8% after 4000 cycles. Furthermore, when combined with a heteroatoms‐doped carbon (HDC) cathode, the HR–BC–Zn//HDC pouch‐type cell exhibits superior lifetime performance with nearly 100% average CE after 15000 cycles at 3.0 A g−1. This work highlights the effectiveness of hydrophilic and insulative coating strategies in fostering the progression of long‐lasting zinc‐based energy storage systems.

Interfacial Lattice Strain‐Induced Vacancy Evolution Facilitating Highly Reversible Dendrite‐Free Zinc Metal Anodes

AbstractInterfacial stress caused by semi‐coherent and incoherent interfaces during zinc (Zn) plating and its effect on subsequent Zn deposition are important considerations for designing electrode/electrolyte interfaces to improve the electrochemical performance of Zn anodes. Although some studies have paid attention to this issue, the influence of lattice strain induced by Zn ion diffusion in the interface coating on Zn deposition is infrequently discussed. Herein, a tin‐doped indium oxide (ITO) interfacial is constructed, and the evolution of interfacial lattice oxygen to vacancy oxygen (OV) induced by lattice stress generated by Zn ion migration in the interface during Zn deposition is confirmed. The formed OV‐rich ITO interface exhibits strong affinity and a low Zn ion diffusion barrier, accelerating the Zn ion transport kinetics. Meanwhile, the interface layer can appropriately capture anions in the electrolyte and improve the corrosion resistance of the electrode through the electrostatic repulsion effect. As a result, the OV‐rich ITO‐decorated Zn anode achieves stable Zn plating/stripping for more than 4500 h and delivers a high average Coulombic efficiency of 99.6% after 1400 cycles at 1.0 mA cm−2. This work provides a new horizon for the rational construction of the interface layer to achieve a highly reversible dendrite‐free Zn metal anode.

A corrosion-resistant zincophilic film enables synergistic hydrogen evolution suppression and dendrite-free deposition toward highly reversible and durable Zn anodes

Zinc ion batteries have challenges originated from the Zn dendrite growth and hydrogen evolution reaction (HER) on Zn anodes. We design an all-in-one corrosion-resistant zincophilic film (CRZF) composed of zinc halide and Cu on Zn (CRZF@Zn) through the replacement reaction of copper halides with Zn metal. The in-situ formed zinc halide with high zincophilicity in the CRZF facilitates desolvation of [Zn(H2O)6]2+ clusters and boosts ions migration, with the conspicuously decreased nucleation potential of Zn. The formed chemically inert Cu improves the corrosion-resistivity of Zn anode and enhances the HER overpotential on Zn. The stimulated charge transfer supports uniform deposition of Zn to avoid the “tip effect”, which effectively restrains dendrites formation on Zn anode. Thus this artificial surface demonstrates synergistic effect on dendrite inhibition and HER suppression. The density functional theory (DFT) calculations show that with the increase of the electronegativity of halogen atoms in the zinc halide, the adsorption energy of Zn2+ on the CRZF layer is enhanced, validating the positive correlation between ions migration and electronegativity of halogen atoms in CRZF. Our findings offer a deeper insight into the interface tuning chemistry of Zn anodes, providing opportunities for the development of dendrite-free and long-life Zn metal batteries.

Stable Zn metal anode enabled via ferroelectric nanotube arrays

Aqueous zinc-ion batteries are receiving increasing attention owing to their markedly high safety and low cost. However, the uncontrolled zinc dendrite growth and the side reactions at Zn-electrolyte interfaces hinder the practical application of aqueous rechargeable zinc-based batteries. Therefore, regulating the electrode/electrolyte interface to achieve dense zinc deposition is crucial for improving the electrochemical performance of zinc-ion batteries. Herein, ferroelectric composite nanotube arrays (BaTiO3 modified TiO2 nanotubes, TiO2@BaTiO3) are designed and fabricated as the three-dimensional current collector for Zn metal anode. Abundant zincophilic sites on the surface of BaTiO3 induce zinc nucleation, enabling a compact and horizontally-aligned Zn morphology. At external electric field, the depolarization field produced the ferroelectric BaTiO3 layer on the electrode surface can accelerate the dissociation of ZnSO4 and regulate the Zn-ion desolvation process at the interfaces, leading to dendrite-free Zn deposition and less byproducts. As a result, the TiO2@BaTiO3/Zn anode achieves reversible Zn plating/stripping with low overpotential for over 3000 h at 3 mA cm−2 in symmetric cells, and the assembled full battery exhibits a significantly enhanced cycling stability over 1800 cycles at 1 A g−1. Ferroelectric nanotube arrays brings new opportunities for next-generation aqueous zinc-ion batteries.

Understanding the hydrogen and halogen bonds of ionic liquids in regulating ion solvation and dynamic behaviors of aqueous zinc electrolytes

Despite their low cost and intrinsic safety, aqueous rechargeable zinc-ion batteries suffer from rapid performance deterioration originating from parasitic reactions and inhomogeneous deposition on the Zn anode. Halogen bonds share similarities with hydrogen bonds, yet their unique directionality, strength tunability, and hydrophobicity provide a promising approach for enhancing the reversibility of Zn anodes. Herein, a systematic comparison of ionic liquids with different anions, acetate (Ac−) and chloride (Cl−), is performed to explore the non-covalent interactions in regulating ion solvation and dynamic behaviors of electrolytes. Different from the Ac− possessing a strong capacity to form hydrogen bonds with water, the Cl−-water halogen bonds not only enable the structural diffusion of Zn2+ with better diffusion efficiency but also reduce the Zn2+ de-solvation energy barrier to promote uniform Zn nucleation. Consequently, the accelerated ions diffusion and homogeneous Zn deposition work in synergy to ensure high reversibility of Zn anode. These fundamental insights highlight the importance of hydrogen and halogen bonds in determining the dynamics and electrochemical behavior of electrolytes, providing theoretical guidance for the rational design of high-performance electrolytes.

Highly reversible Zn anodes enabled by in-situ construction of zincophilic zinc polyacrylate interphase for aqueous Zn-ion batteries

The irreversibility and low utilization of Zn anode stemming from the corrosion and dendrite growth have largely limited the commercialization of aqueous zinc batteries. Here, a carbonyl-rich polymer interphase of zinc polyacrylate (ZPAA) is spontaneously in-situ constructed on Zn anode to address the above-mentioned dilemmas. The ZPAA interlayer enables fast transport kinetics of Zn2+ and tailors the interfacial electric field for realizing the uniform Zn deposition due to superior zincophilicity, high Zn2+ transference number and inherent ion-diffusion channel. Importantly, acting as a buffer interphase with strong adhesion and isolation of electrolytes, this functional layer effectively protects the Zn electrode against the water-induced erosion and passivation. Remarkably, the ZPAA@Zn electrode realizes an enhanced Coulombic efficiency of 99.71 % within 2200 cycles, delivers an ultra-long cycling stability over 7660 h (>319 days, 1 mA cm−2) and 2460 h (5 mA cm−2) with lower voltage hysteresis. Also, the ZPAA@Zn/MnO2 full cell maintains a high capacity of 114 mAh/g after 2000 cycles, much better that of untreated Zn/MnO2 cell (25 mAh/g). This concept of in-situ fabricating ion-sieve-like polymer interphase provides a facile approach to stabilize Zn anode and further paves a way for high-performance aqueous batteries.

Two-episode mineralization in the Haerdaban Pb–Zn deposit, NW China: Insights from sulfide trace elements, in situ S–Pb isotopes, and Rb–Sr geochronology

The Haerdaban Pb–Zn deposit, located in the eastern West Tianshan Orogen, hosts stratiform and vein-type mineralization within Precambrian carbonate rocks. However, there has been limited research on the distinctions and relationships between these two mineralization styles. In this study, we compared trace element distributions, fluid conditions, material sources, and mineralization ages between stratiform and vein-type mineralization and reconstructed a detailed genetic model. Two episodes and four stages of mineralization were identified, including five generations of pyrite and two generations of sphalerite. The sedimentary exhalative episode represents stratiform mineralization including Stage I pyrite–pyrrhotite layers (Py-1, Py-2a, Py-2b, and Py-3) and Stage II sphalerite–galena layers (Sph-1). The magmatic–hydrothermal episode represents vein-type mineralization including Stage III pyrite–quartz–calcite veins (Py-4) and Stage IV sphalerite–galena–quartz–calcite veins (Sph-2). LA–ICP–MS analysis of Se–Co–Ni–As–Ag–Sb–Bi contents in pyrite suggests that Py-1 to Py-3 formed under relatively low temperatures (280 ± 8 °C) and high ƒO2 sedimentary conditions. Py-4 formed under relatively high temperatures (339 ± 18 °C) and low ƒO2 hydrothermal conditions. Variations in Fe–Mn–In–Ga–Ge–Cd–Cu contents in sphalerite indicate that Sph-1 formed under relatively low temperature (211 ± 7 °C), intermediate ƒS2 (logƒS2 = −11.1 ± 0.5), and moderate pH sedimentary exhalative conditions. Sph-2 formed under relatively high temperature (292 ± 5 °C), high ƒS2 (logƒS2 = −7.4 ± 0.2), and low pH hydrothermal conditions. In situ analysis of sulfide S–Pb suggests that ore-forming materials for stratiform mineralization were primarily derived from marine sediments, while those for vein-type mineralization primarily originated from magmatic sources. Sph-1 from stratiform mineralization yielded an Rb–Sr isochron age of 719 ± 16 Ma, while Sph-2 from vein-type mineralization exhibited an Rb–Sr isochron age of 380.3 ± 7.7 Ma. Random Forest classification of trace elements in pyrite and sphalerite predicted that stratiform mineralization is of sedimentary genesis, whereas vein-type mineralization is of magmatic–hydrothermal genesis. Based on our results, we identified a two-episode mineralization history for the Haerdaban Pb–Zn deposit: Neoproterozoic syngenetic sedimentary exhalative mineralization overprinted by Devonian epigenetic magmatic–hydrothermal mineralization. The results of this study highlight the importance of considering multiple geological events in ore-forming processes and will facilitate the exploration of similar deposits in the West Tianshan Orogen.

A Cu-Zn bimetallic organic framework as protective interlayer for dendrite-free Zn deposition in zinc-based flow batteries

Zinc-based flow batteries hold great promise for grid-scale energy storage. However, the formation of zinc dendrites challenges their lifespan and safety. In this work, we devise a bimetallic organic framework material on carbon cloth (CuZn@MOF-CC) using a one-step dip coating method to address the dendrite issue. The prepared CuZn@MOF-CC promotes the creation of zincophilic sites on the electrode surface, facilitating smooth and uniform zinc deposition. Electrochemical csharacterizations and density functional theory (DFT) calculations reveal much stronger electronic interactions between CuZn@MOF and the zinc atoms compared to the commonly used anode material through an obvious electron interaction between the Zn atom and the Cu sites linked in the CuZn@MOF chain. By mitigating the zinc dendrite problem, this approach effectively improves the coulombic efficiency, cycle life, and safety of zinc-based flow batteries. The battery incorporating the prepared material demonstrates impressive stability, exceeding 450 cycles without dendrites at a high current density of 320 mA cm−2, paving the way for efficient and reliable energy storage solutions and a sustainable future.

Homogeneous Deposition of Zinc on N-Doped Carbon Fibers Interconnected with Sn Nanoparticles for Advanced Aqueous Zinc Batteries.

Currently, inhomogeneous distribution of Zn2+ on the surface of the Zn anode is still the essential reason for dendrite formation and unsatisfactory stability of zinc ion batteries. Given the merits of strong interaction between Sn and Zn, as well as a low nucleation barrier during Zn deposition, the combination of metallic Sn with carbon material is expected to improve the deposition of zinc ions and inhibit the growth of zinc dendrites by guiding the homogeneous plating/stripping of zinc on the electrode surface. In this article, zincophilic Sn nanoparticles with low nucleation barriers and strong interaction with Zn2+ were embedded into 3D N-doped carbon nanofibers using a simple electrostatic spinning technique. Accordingly, when serving as an artificial coating layer for the zinc metal anode, an ultrastable Sn@NCNFs@Zn||Sn@NCNFs@Zn symmetric cell can be achieved for over 3500 h with a low nucleation overpotential of 29.1 mV. Significantly, the full cell device assembled with the as-prepared anode and MnO2 cathode exhibits desirable electrochemical behaviors. Moreover, this simple method could be extended to other metal-carbon composites, and to ensure ease in scaling up as required. Such significant approach can provide an effective strategy for the design of high-performance zinc anodes.

Highly reversible Zn anode by guiding uniform Zn deposition through LiF protective layer

Deep-seated issues such as ineluctable dendrite deposition and parasitic reaction of Zn anode pose a major obstacle to the commercialization of aqueous zinc ion batteries (AZIBs). Herein, we proposed LiF as a solid-electrolyte interphase for highly reversible Zn anode. Combining experimental analyses and theoretical simulation calculations, the electronegative fluorine atoms could provide uniform zincophilic nucleation sites to regulate Zn deposition behavior. Additionally, a ZnF2 layer with outstanding Zn2+ conductive can be formed insitu thus further shielding bulk water molecules and expediting the Zn2+ transfer kinetics. Therefore, the LiF@Zn symmetric cells manifest long-cycling stability with 650 h at 1.0 mA/cm2 and 1.0 mAh/cm2 and 1000 h at 2.0 mA/cm2 and 1.0 mAh/cm2. Meanwhile, the rate performance of Zn//MnO2 and Zn//NH4V4O10 full cells are also enhanced by the LiF coating. This work provides a horizon for the design of artificial protective layer and promotes the large-scale practical development of AZIBs.

Water‐Lean Inner Helmholtz Plane Enabled by Tetrahydropyran for Highly Reversible Zinc Metal Anode

AbstractThe reversibility and stability of zinc (Zn) metal anode are closely related to inner Helmholtz plane (IHP) chemistry. The H2O‐rich IHP raises severe parasitic reactions and irregular Zn deposition, impeding the practical utility of Zn anode in aqueous Zn‐ion batteries (AZIBs). In this study, tetrahydropyran (THP), a five‐carbon heterocyclic ether with permanent dipole moment and hydrophobic characteristic, is introduced as a self‐adsorptive additive to reshape the IHP. It squeezes out partial H2O molecules and forms a H2O‐lean IHP, benefitting for alleviating active H2O decomposition and improving the stability of Zn anode. Moreover, the adsorbed THP induces the preferential nucleation of Zn (002) plane, facilitating dendrite‐free growth and improving the reversibility of Zn anode. Consequently, the Zn||Zn symmetric cell enables to cycle over 3600 h at 5 mA cm−2@ 1 mAh cm−2. The Zn||Cu half‐cell can stably cycle over 400 cycles with 99.9% coulombic efficiency even under harsh test conditions (10 mA cm−2@5 mAh cm−2) with 30 µm Zn foil. The Zn||NH4V4O10 full cell maintains 92.6% capacity retention after 800 cycles at 1 A g−1 and the Zn||I2 full cell enables to perform steadily over 10000 cycles with a capacity decay rate of merely 0.003% per cycle at 5 C.

The superposition of Cretaceous mineralization events leading to the formation of the large Baiyinnuoer Pb–Zn deposit in NE China

The Baiyinnuoer Pb–Zn deposit, estimated at 26.57 million metric tonnes (Mt) with grades of 1.77% Pb and 5.21% Zn, is situated in the southern Great Xing'an Range (SGXR) of northeast China. The deposit comprises southern and northern ore belts. The southern belt primarily contains skarn ore bodies (32% of reserves) associated with Triassic granodiorite, while the northern belt is dominated by skarn ore bodies (30% of reserves) related to Triassic diorite porphyry. In addition to Triassic skarn‐type mineralization, the deposit also exhibits Early Cretaceous mineralization. This includes vein‐type occurrences (36% of reserves) within volcanic tuff and syenite porphyry, alongside a small amount of skarn ore bodies (2% of reserves) related to syenite porphyry. LA‐ICP‐MS U–Pb dating of intrusive rocks and garnets was conducted to investigate the timing and genesis of these mineralization events, revealing two distinct stages of skarn‐type mineralization. The first stage, associated with Early Triassic granitoids, dates to 254.6 ± 1.4–241.7 ± 2.7 Ma, while the second stage is closely associated with Early Cretaceous syenite porphyry, constrained to 135.4 ± 1.1–135.2 ± 1.6 Ma. Garnet U–Pb dating in the syenite porphyry‐related skarn yielded an age of 134.9 ± 4.7 Ma; however, due to low U content, reliable dating of garnets associated with Early Triassic granitoid‐related skarn was not feasible. Micro‐thermometry and Laser Raman analyses of fluid inclusions within vein‐type ore bodies highlighted distinct differences between vein‐type mineralization and Early Triassic skarn‐type mineralization. Additionally, in situ sulfur isotope analyses of sphalerite from both Early Triassic and Early Cretaceous ore bodies indicate a magmatic origin for sulfur in both stages. Through comprehensive geological, geochronological, in situ sulfur isotope and fluid inclusion studies, the Baiyinnuoer Pb–Zn deposit is conclusively identified as a large deposit characterized by two distinct periods of mineralization (Early Triassic and Early Cretaceous), akin to several other significant polymetallic deposits in NE China.

Sieving-type Electric Double Layer with Hydrogen Bond Interlocking to Stable Zinc Metal Anode.

The stability of aqueous zinc metal batteries is significantly affected by side reactions and dendrite growth on the anode interface, which primarily originate from water and anions. Herein, we introduce a multi H-bond site additive, 2, 2'-Sulfonyldiethanol (SDE), into an aqueous electrolyte to construct a sieving-type electric double layer (EDL) by hydrogen bond interlock in order to address these issues. On the one hand, SDE replaces H2O and SO42- anions that are adsorbed on the zinc anode surface, expelling H2O/SO42- from the EDL and thereby reducing the content of H2O/SO42- at the interface. On the other hand, when Zn2+ are de-solvated at the interface during the plating, the strong hydrogen bond interaction between SDE and H2O/SO42- can trap H2O/SO42- from the EDL, further decreasing their content at the interface. This effectively sieves them out of the zinc anode interface and inhibits the side reactions. Moreover, the unique characteristics of trapped SO42- anions can restrict their diffusion, thereby enhancing the transference number of Zn2+ and promoting dendrite-free deposition and growth of Zn. Consequently, utilizing an SDE/ZnSO4 electrolyte enables excellent cycling stability in Zn//Zn symmetrical cells and Zn//MnO2 full cells with lifespans exceeding 3500 h and 2500 cycles respectively.

Achieving high-durability aqueous Zn-ion batteries enabled by reanimating inactive Zn on Zn anodes

The heavy by-products generated on Zn anode surface decrease the active surface of Zn anodes and thus induce uneven Zn deposition, seriously reducing the service life of aqueous Zn-ion batteries (AZIBs). Herein, we propose an elimination strategy enabled by the coordination chemistry to dissolve the main by-products (Zn4SO4(OH)6·xH2O). Urea as a proof-of-concept has been applied as the reactivator in the electrolyte to catalytically produce highly active NH3 on the surface of the by-products. Then the NH3 can powerfully coordinate with the Zn2+ ion in the by-products to form the soluble complex [Zn(NH3)4]2+. Consequently, the proposed electrolyte can not only lead to the timely decomposition of the by-products to prevent the Zn anode from inactivation during cycling, but also repair the waste Zn anodes for reutilization. The action mechanism has been systematically demonstrated via theoretical simulation and experimental study. As a result, the high durability with ultrahigh cumulative capacity of 10,600 mAh cm−2 for the Zn||Zn symmetric cell has been achieved at 40 mA cm−2. Particularly, the dead Zn||Zn symmetric cells and Zn||LiFePO4 full cells have been successfully reactivated. This study lights a new route to extend the cell lifespan and reuse waste Zn-ion batteries.

Regulating zinc hydroxide sulfate (0 0 1) preferential growth and Zn (0 0 2) deposition by trace dibenzenesulfonimide additive toward long cycle lifespan for aqueous Zn-ion batteries

Regulating the zinc hydroxide sulfate (ZHS) growth orientation to construct interface layer with electronic insulation and high flux of Zn2+ is an efficient way to suppress parasitic side reactions and Zn dendrite in rechargeable aqueous zinc-ion batteries (ZIBs). Herein, a novel ZnSO4-based electrolyte with dibenzenesulfonimide (BBI) additive is proven able to maintain long-time cycle stabilities of Zn anode. The combination of experimental and precise testing technologies demonstrated that BBI additive can guide a surface-preferred ZHS (001) and Zn (002) crystal plane, as well as prevent the Zn corrosion and dendrite growth to smooth Zn deposition by adjusting the solid-phase interface energy. As a result, the Zn||Cu cells deliver an extended cycling lifespan over 1500 cycles with 99.7 % Coulombic efficiency at the current density of 2 mA cm−2, demonstrating an ultra-stable plating/stripping behavior. More encouragingly, the cyclic stability of Zn-MnO2 battery with the ZnSO4-BBI electrolyte can deliver a specific capacity of ∼165 mAh g−1 after 200 cycles at 1 C. This study clearly elucidates the interface behaviors to stabilize Zn anode, which contributes to a deep insight into the additive regulation mechanisms and brings a promising approach to solve the anode nuisance in aqueous metal batteries.

Improvements and Challenges of Hydrogel Polymer Electrolytes for Advanced Zinc Anodes in Aqueous Zinc-Ion Batteries.

Aqueous zinc-ion batteries (AZIBs) are widely regarded as desirable energy storage devices due to their inherent safety and low cost. Hydrogel polymer electrolytes (HPEs) are cross-linked polymers filled with water and zinc salts. They are not only widely used in flexible batteries but also represent an ideal electrolyte candidate for addressing the issues associated with the Zn anode, including dendrite formation and side reactions. In HPEs, an abundance of hydrophilic groups can form strong hydrogen bonds with water molecules, reducing water activity and inhibiting water decomposition. At the same time, special Zn2+ transport channels can be constructed in HPEs to homogenize the Zn2+ flux and promote uniform Zn deposition. However, HPEs still face issues in practical applications, including poor ionic conductivity, low mechanical strength, poor interface stability, and narrow electrochemical stability windows. This Review discusses the issues associated with HPEs for advanced AZIBs, and the recent progresses are summarized. Finally, the Review outlines the opportunities and challenges for achieving high performance HPEs, facilitating the utilization of HPEs in AZIBs.