Zn Deposits Research Articles

Dendrite-free electrolyte for Zn/LiFePO4 batteries operating at low-temperature

Zinc-ion batteries, known for safety and efficiency, are a hotspot in electrochemical energy storage field. Nonetheless, the emergence of dendrites on zinc anodes during electrochemical cycles can lead to capacity attenuation and even failure, particularly under low temperatures. In this study, we develop a novel dendrite-free and low-temperature resistant Zn(ClO4)2/Li2SO4/Dimethyl sulfoxide (DMSO) hybrid electrolyte by using DMSO as a hydrogen bond acceptor and solvation regulator. Our research demonstrates that, by reducing the desolvation energy barrier of the Zn2+ solvation sheath and the nucleation overpotential of Zn deposition, DMSO effectively inhibits zinc dendrites and side reactions. Furthermore, DMSO disrupts hydrogen bonding between water molecules, preventing electrolyte freezing at low temperatures. As a result, at 0.5 mA cm−2, the Zn||Zn symmetric device using this hybrid electrolyte exhibits consistent operation for over 4000 h even at -25 °C, featuring a minimal deposition/dissolution overpotential of approximately 0.045 mV. Additionally, at -20 °C, the Zn||Zn(ClO4)2-Li2SO4-DMSO||LiFePO4 battery demonstrates stable cycling for over 600 cycles at 0.6 C (1 C = 170 mA g− 1), delivering a capacity of 103 mA h g−1.

Dual-functional ionic liquids additive enables dendrite-free Zn anode with ultra-long cycle life over one year

Zn anodes suffer from the formation of uncontrolled dendrites aggravated by the uneven electric field and the insulating by-product accumulation in aqueous zinc-ion batteries (AZIBs). Here, an effective strategy implemented by 1-butyl-3-methylimidazolium hydrogen sulfate (BMIHSO4) additive is proposed to synergistically tune the crystallographic orientation of zinc deposition and suppress the formation of zinc hydroxide sulfate for enhancing the reversibility on Zn anode surface. As a competing cation, BMI+ is proved to preferably adsorb on Zn-electrode compared with H2O molecules, which shields the “tip effect” and inhibits the Zn-deposition agglomerations to inducing the horizontal growth along Zn (002) crystallographic texture. Simultaneously, the protonated BMIHSO4 additives could remove the detrimental OH– in real-time to fundamentally eliminate the accumulation of 6Zn(OH)2·ZnSO4·4H2O and Zn4SO4(OH)6·H2O on Zn anode surface. Consequently, Zn anode exhibits an ultra-long cycling stability of one year (8762 h) at 0.2 mA cm−2/0.2 mAh cm−2, 3600 h at 2 mA cm−2/2 mAh cm−2 with a high plating cumulative capacity of 3.6 Ah cm−2, and a high average Coulombic efficiency of 99.6 % throughout 1000 cycles. This work of regulating Zn deposition texture combined with eliminating notorious by-products could offer a desirable way for stabilizing the Zn-anode/electrolyte interface in AZIBs.

“Co-solvent-in-salt” electrolyte for boosting Zn anode reversibility

The “solvent-in-salt” electrolyte is considered as a technology of significance for rechargeable Zn metal batteries due to its non-flammable, moisture-tolerant and electrochemical stable merits. Particularly, the “co-solvent-in-salt” electrolyte with dual-solvent of water and acetonitrile is developed in this work. It possesses both the advantages of high-concentration and aqueous/organic hybrid solvent, such as, low cost, low water content, high concentration and impressive ion conductivity. The corresponding modulated solvation structure and chemical environmental in the optimized electrolyte system contribute to suppress the side reactions (hydrogen evolution reaction (HER), Zn corrosion, dendrites growth) significantly. And they further improve the homogeneous Zn deposition, the plating/stripping reversibility (∼99.8 %) and the stability (∼2900 h) of Zn metal anode even in the Zn//NH4V4O10 full battery (500 cycles).

Cd–Pb isotopic characteristics within the Hehuashan carbonate-hosted Pb–Zn deposit, Middle-Lower Yangtze River Metallogenic Belt: Constraints for ore-forming metal sources and implications for exploration

The Hehuashan carbonate-hosted Pb–Zn deposit is a large-scale deposit situated in the Middle-Lower Yangtze-River Metallogenic Belt (MLYRMB) in China. It contains 0.99 million tons of Zn at an average grade of 1.5 % and 0.41 million tons of Pb at an average grade at 1.9 %, accompanied by critical metals of Cd and Ga. The ores are mainly composed of breccia-type and vein-type in the deposit. Though previous chemical compositions of sphalerite showed that Cd is enriched in both two types of mineralization and the sulfide sulfur isotopes research showed that the reduced sulfur is derived from the marine sulfate reduction, the source of ore-forming metals is still unclear. In this research, we studied the non-traditional stable isotope of Cd and the radioactive isotope Pb of the Hehuashan deposit to discuss the ore-forming metal sources and provide genesis constraints to the Hehuashan Pb–Zn deposit. The sphalerite Cd isotopic compositions are relatively concentrated but the Zn/Cd ratios are scattered in the Hehuashan deposit, of which the early-stage sphalerite δ114/110Cd values ranged from 0.21 ‰ to 0.30 ‰ with an outlier of 0.09 ‰, mean of 0.22 ‰ and a wide range of Zn/Cd ratios (78 to 430), and the late-stage sphalerite δ114/110Cd values ranged from 0.09 ‰ to 0.15 ‰ with two outliers of −0.05 ‰ and 0.52 ‰, mean of 0.17 ‰ with also a wide range of Zn/Cd ratios (50 to 286), both stages of Cd isotopic compositions are overlapped with the ranges of diorite and OIB & MORB, implying the Cd is might be derived from the dioritic intrusions of the Hehuashan deposit district, and the varied Zn/Cd ratios imply that the limestone also provided some of ore-forming metals to the both two ore-forming stages. Additionally, the Pb isotopic compositions of galena in the two mineralization stages exhibit a concentrated range (206Pb/204Pb = 18.2806 – 18.4190, 207Pb/204Pb = 15.6262 – 15.6484, and 208Pb/204Pb = 38.5710 – 38.6529) and all the Pb isotopic data points of the Hehuashan deposit are plotted in the right-hand side of the geochron and the overlapped field of marine sediments, Tongling dioritic intrusions, and Lower Triassic limestones in the Tongling area in the diagrams of (207Pb/204Pb)i vs. (206/204Pb)i and in the field (208Pb/204Pb)i vs. (206/204Pb)i, implying that the Pb is mainly derived from the magma of dioritic intrusions and marine sediments. Subsequently, the sulfide Cd–Pb isotopic compositions show that the ore-forming metals in the Hehuashan deposit are mainly originated from the dioritic intrusions and marine sediments. The plots of deposit genesis classification show that the Cd isotopic compositions in the Hehuashan deposit are unsuitable to the plots of δ114/110Cd vs. Zn/Cd ratios, but imply the metals were derived from multi sources. Finally, the Cd-Pb studies of the Hehaushan Pb–Zn deposit show that the earlier Lower Triassic carbonate formations and its contact with dioritic rocks should be ideal exploration targets for Pb–Zn and associated Cd sources in the Tongling mining area.

In Situ Constructing Metal-Organic Complex Interface Layer Using Biomolecule Enabling Stabilize Zn Anode.

Aqueous zinc-ion batteries (ZIBs) are considered as a promising candidate for next-generation large-scale energy storage due to their high safety, low cost, and eco-friendliness. Unfortunately, commercialization of ZIBs is severely hindered owing to rampant dendrite growth and detrimental side reactions on the Zn anode. Herein, inspired by the metal-organic complex interphase strategy, the authors apply adenosine triphosphate (ATP) to in situ construct a multifunctional film on the metal Zn surface (marked as ATP@Zn) by a facile etching method. The ATP-induced interfacial layer enhances lipophilicity, promoting uniform Zn2+ flux and further homogenizing Zn deposition. Meanwhile, the functional interlayer improves the anticorrosion ability of the Zn anode, effectively suppressing corrosion and hydrogen evolution. Consequently, the as-prepared ATP@Zn anode in the symmetric cell exhibits eminent plating/stripping reversibility for over 2800h at 5.0mA cm-2 and 1 mAh cm-2. Furthermore, the assembled ATP@Zn||MnO2 full cells are investigated to evaluate practical feasibilities. This work provides an efficient and simple strategy to prepare stabilized Zn anode toward high-performance ZIBs.

Alleviating zinc dendrite growth by versatile sodium carboxymethyl cellulose electrolyte additive to boost long-life aqueous Zn ion capacitors

Zn ion capacitors (ZICs) have become a strong candidate for energy storage equipment because the advantages of environment friendly, high safety, low cost. However, the Zn anode suffers from severe dendrite growth and irreversible side reactions, resulting in a short cycle life of ZICs. In this work, a green and low-cost sodium carboxymethyl cellulose (CMC-Na) is used as an additive in ZnSO4 electrolyte. The density functional theory calculations and molecular dynamics simulations demonstrate that CMC-Na can effectively optimize the electrolyte environment and regulate the electrode-electrolyte interface. Among them, Na+ has a lower redox site compared to Zn2+, Na+ can be reduced preferentially to Zn2+, the formation of the electrostatic protection layer can inhibit the formation of differential electric field and promote the uniform distribution of the electric field, which is conducive to the homogenization of the nucleation sites of the Zn deposition layer. The organic molecules contain abundant hydrophilic groups (OH, COO−), which can effectively optimize the structure of Zn2+ solvation sheath by destroying the hydrogen bonding network in the environment of ZnSO4 electrolyte, thus reducing the rate of side reactions and the random growth of dendrites will be suppressed. And the Zn//Zn cells with ZnSO4+CMC-Na(0.13) electrolyte enable to perform a stable cycle over 1600 h (at 4 mA cm−2 with a capacity of 1 mAh cm−2), which is vastly superior that of without additive (only 70 h). The results confirm that the import of CMC-Na additive into the ZnSO4 electrolyte can effectively prevent side reaction and achieve uniform deposition of Zn dendrites. The low-cost electrolyte additive provides an innovative strategy or the protection of Zn metal electrode in aqueous electrochemical energy storage devices.

Converting Commercial Zn Foils into Single (002)‐Textured Zn with Millimeter‐Sized Grains for Highly Reversible Aqueous Zinc Batteries

AbstractRechargeable aqueous zinc batteries are promising but hindered by unfavorable dendrite growth and side reactions on zinc anodes. In this study, we demonstrate a fast melting‐solidification approach for effectively converting commercial Zn foils into single (002)‐textured Zn featuring millimeter‐sized grains. The melting process eliminates initial texture, residual stress, and grain size variations in diverse commercial Zn foils, guaranteeing the uniformity of commercial Zn foils into single (002)‐textured Zn. The single (002)‐texture ensures large‐scale epitaxial and dense Zn deposition, while the reduction in grain boundaries significantly minimizes intergranular reactions. These features enable large grain single (002)‐textured Zn shows planar and dense Zn deposition under harsh conditions (100 mA cm−2, 100 mAh cm−2), impressive reversibility in Zn||Zn symmetric cell (3280 h under 1 mA cm−2, 830 h under 10 mAh cm−2), and long cycling stability over 180 h with a high depth of discharge value of 75 %. This study successfully addresses the issue of uncontrollable texture formation in Zn foils following routine annealing treatments with temperatures below the Zn melting point. The findings of this study establish a highly efficient strategy for fabricating highly reversible single (002)‐textured Zn anodes.

Converting Commercial Zn Foils into Single (002)-Textured Zn with Millimeter-Sized Grains for Highly Reversible Aqueous Zinc Batteries.

Rechargeable aqueous zinc batteries are promising but hindered by unfavorable dendrite growth and side reactions on zinc anodes. In this study, we demonstrate a fast melting-solidification approach for effectively converting commercial Zn foils into single (002)-textured Zn featuring millimeter-sized grains. The melting process eliminates initial texture, residual stress, and grain size variations in diverse commercial Zn foils, guaranteeing the uniformity of commercial Zn foils into single (002)-textured Zn. The single (002)-texture ensures large-scale epitaxial and dense Zn deposition, while the reduction in grain boundaries significantly minimizes intergranular reactions. These features enable large grain single (002)-textured Zn shows planar and dense Zn deposition under harsh conditions (100 mA cm-2, 100 mAh cm-2), impressive reversibility in Zn||Zn symmetric cell (3280 h under 1 mA cm-2, 830 h under 10 mAh cm-2), and long cycling stability over 180 h with a high depth of discharge value of 75 %. This study successfully addresses the issue of uncontrollable texture formation in Zn foils following routine annealing treatments with temperatures below the Zn melting point. The findings of this study establish a highly efficient strategy for fabricating highly reversible single (002)-textured Zn anodes.

Sodium Citrate Electrolyte Additive to Improve Zinc Anode Behavior in Aqueous Zinc-Ion Batteries

Despite features of cost-effectiveness, high safety, and superior capacity, aqueous zinc-ion batteries (ZIBs) have issues of uncontrolled dendritic cell failure and poor Zn utilization, resulting in inferior cycling reversibility. Herein, the environmentally friendly and naturally abundant sodium citrate (SC) was adopted as a dual-functional additive for ZnSO4-based (ZSO) electrolytes. Owing to the abundant hydrogen-bond donors and hydrogen-bond acceptors of SC, the Zn2+-solvation shell is interrupted to facilitate Zn desolvation, resulting in inhibited corrosion reactions. Additionally, sodium ions (Na+) from the SC additive with a lower effective reduction potential than that of zinc ions (Zn2+) form an electrostatic shield inhibiting the formation of initial surface protuberances and subsequent Zn dendrite growth. This assists in the Zn three-dimensional (3D) diffusion and deposition, thereby effectively enhancing cycling stability. Specifically, a long cycling lifespan (more than 760 h) of the Zn//Zn symmetric cell is achieved with a 2 M ZSO-1.0 SC electrolyte at a current density of 1 mA cm−2. When coupled with the NaV3O8·1.5 H2O (NVO) cathode, the full battery containing SC additive exhibited a capacity retention rate (40.0%) and a cycling life of 400 cycles at a current density of 1 A g−1 compared with that of pure ZnSO4 electrolyte (23.8%). This work provides a protocol for selecting an environmentally friendly and naturally abundant dual-functional electrolyte additive to achieve solvation shell regulation and Zn anode protection for the practical large-scale application of ZIBs.

Major types, spatio-temporal distribution, and metallogenesis of magmatism-related polymetallic deposits in the Bangonghu–Nujiang metallogenic belt, Tibet

The Bangong–Nujiang metallogenic belt (BNMB) is one of the vital metallogenic belts in the Tibetan Plateau. At present, the metallogenic regularity on the scale of the whole metallogenic belt is still poorly understood. In this contribution, the geological, geochronological, geochemical, and isotopic data of 87 magmatism-related polymetallic deposits in the BNMB have been systematically collected to summarize the metallogenesis of polymetallic deposits in this belt. Our research shows that different segments of the BNMB have distinct metallogenic differences. The western, central, and eastern segments of the BNMB are characterized by the development of abundant Cu–Au, Fe–Cu–Cr–Ni, and W–Pb–Zn deposits, respectively. These various types of magmatism-related polymetallic deposits in the BNMB were formed between 188 Ma and 76 Ma, and the mineralization has two peak periods of 125–110 Ma and 90–75 Ma. The spatio-temporal variation of different types of magmatism-related polymetallic deposits in the BNMB is likely to be constrained by the lithospheric architecture and deep geodynamic processes. The elemental and Sr–Nd–Hf–S–Pb isotopic results indicate that various kinds of mineralization are closely related to relevant magmatism. The Cu–Au mineralization is related to dominantly mantle-derived, highly-oxidized, and less-evolved granitic intrusions; the Pb–Zn–W mineralization is genetically associated with dominantly ancient middle–upper crust-derived, relatively reduced, and highly-evolved granitic intrusions; the characteristics of the ore-causative intrusions related to Fe–Cu–Mo polymetallic mineralization are between those of the above two end members. In combination with previous studies, we propose a comprehensive model that includes four stages (>145 Ma, ∼145–125 Ma, ∼125–105 Ma, and ∼105–74 Ma) to illustrate the Jurassic–Cretaceous tectonic–magmatic–metallogenic evolution history in the whole BNMB.

In-situ constructed solvated carbon quantum dot clusters to achieve uniform Zn plating in aqueous zinc ion batteries

Zinc ion batteries (ZIBs) have become the most competitive candidates for the next-generation energy storage systems due to its low-price, good safety and high theoretical capacity. However, the uncontrollable dendrite growth and parasitic side reactions still hinder the practical application of the zinc ion batteries. Herein, a hybrid functionalized carbon quantum dots (FCQDs)/ZnSO4 electrolyte is in-situ synthesized via a simple one-pot hydrothermal method with glucose as precursor. The created FCQDs possess abundant anionic groups like hydroxyl, carboxyl and sulfonic acid groups, and those anionic groups can strongly absorb Zn2+ ions and then the FCQDs, Zn2+ and water molecules together generate a special solvation structure of solvated carbon quantum dot clusters [FCQDsZnx(H2O)y]2x+. The solvated FCQDs clusters can help to in-situ induce the uniform Zn deposition through a co-plating of Zn atoms and the functionalized FCQDs. Additionally, this unique solvation structure promotes easier dissociation of solvation water molecules, thus decreasing the de-solvation energy. The lower de-solvation energy barrier can help to restrain the water decomposition and the related by-products. Benefiting from the construction of this unique solvated FCQDs clusters, the hybrid electrolyte with FCQDs endows a better performance of both Zn||Zn symmetric cells and full ZIBs.

Ion‐Sieving Effect Enabled by Sulfonation of Cellulose Separator Realizing Dendrite‐Free Zn Deposition

AbstractAqueous zinc‐ion batteries (AZIBs) hold great potential for grid‐scale energy storage systems, owing to their intrinsic safety and low cost. Nevertheless, their industrialization faces challenges of severe Zn dendrites and parasitic reactions. In this study, sulfonated cellulose separator (denoted as CF‐SO3) with low thickness, exceptional mechanical strength, and large ionic conductivity is developed. Benefiting from the electrostatic repulsion between ─SO3− functional groups and SO42− anions and the strongly interaction between ─SO3− and Zn2+ cations, the migration of SO42− anions can be restricted, the 2D diffusion of Zn2+ ions at the surface of Zn electrode can be suppressed, and the desolvation of hydrated Zn2+ ions can be promoted. Concurrently, the homogeneous nanochannels within CF‐SO3 separator can ensure uniform electric field and Zn2+ ion flux. With these benefits, the CF‐SO3 separator enables Zn//Zn cells to run stably for 1200 h at 4 mAh cm−2 by facilitating oriented and dendrite‐free Zn deposition. Under a large depth of discharge of 68.3%, a life span of 400 h can still be achieved. Additionally, the reliability of CF‐SO3 separator is confirmed in Zn//MnO2 and Zn//H11Al2V6O23.2 full batteries with high mass loading conditions. This work provides valuable guidance for the advancement of high‐performance separators of AZIBs.

A self-regulated interface enabled by trivalent gadolinium ions toward highly reversible zinc metal anodes

Aqueous zinc-ion batteries (AZIBs) have become an ideal candidate for large-scale energy storage systems owing to their inherent safety and highly competitive capacity. However, severe dendrite growth and side reactions on the surface of zinc metal anodes lead to quick performance deterioration, seriously impeding the commercialization of AZIBs. In this work, a self-regulated zinc metal/electrolyte interface is constructed to solve these problems by incorporating the trivalent Gd3+ additive with a lower effective reduction potential into the aqueous ZnSO4 electrolyte. It is revealed that the inert Gd3+ ions preferentially adsorb on the active sites of the zinc anode, and the induced electrostatic shielding layer is beneficial to uniform Zn deposition. Meanwhile, the adsorbed Gd3+ ions act as a buffer interface to lower the direct contact of the zinc anode with water molecules, thereby suppressing the interfacial parasitic reaction. These features endow the Zn//Zn battery using 0.2 M Gd3+ ions with 2940 h of cycling life at 5 mA cm−2 and a cumulative plating capacity (CPC) of 6.2 Ah cm−2 at 40 mA cm−2. When assembling with a MnO2 cathode, the full cell using the modified electrolyte exhibits a high capacity of 268.9 mAh/g at 0.2 A/g, as well as improved rate capability and cycle stability. The results suggest the great potential of a rare earth ion additive in reinforcing Zn metal anodes for developing practical AZIBs.

Dendrite‐free Zn deposition initiated by nanoscale inorganic–organic coating‐modified 3D host for stable Zn‐ion battery

AbstractA 3D nanostructured scaffold as the host for zinc enables effective inhibition of anodic dendrite growth. However, the increased electrode/electrolyte interface area provided by using 3D matrices exacerbates the passivation and localized corrosion of the Zn anode, ultimately bringing about the degradation of the electrochemical performance. Herein, a nanoscale coating of inorganic–organic hybrid (α‐In2Se3‐Nafion) onto a flexible carbon nanotubes (CNTs) framework (ISNF@CNTs) is designed as a Zn plating/stripping scaffold to ensure uniform Zn nucleation, thus achieving a dendrite‐free and durable Zn anode. The introduced inorganic–organic interfacial layer is dense and sturdy, which hinders the direct exposure of deposited Zn to electrolytes and mitigates the side reactions. Meanwhile, the zincophilic nature of ISNF can largely reduce the nucleation energy barrier and promote the ion‐diffusion transportation. Consequently, the ISNF@CNTs@Zn electrode exhibits a low‐voltage hysteresis and a superior cycling life (over 1500 h), with dendrite‐free Zn‐plating behaviors in a typical symmetrical cell test. Additionally, the superior feature of ISNF@CNTs@Zn anode is further demonstrated by Zn‐MnO2 cells in both coin and flexible quasi‐solid‐state configurations. This work puts forward an inspired remedy for advanced Zn‐ion batteries.

Hydrophilic‐Zincophobic Separator Enabling by Crystal Structure Regulation toward Stabilized Zn Metal Anode

AbstractAqueous zinc‐ion batteries (ZIBs) hold significant promise for large‐scale energy storage. While considerable strides have been made in modifying separators, the challenge of developing dendrite‐free, corrosion‐resistant, and cost‐effective separators for achieving extended cycling performance of Zn anodes persists. In light of this, a TiO2 coating separator to mitigate interfacial corrosion and passivation reactions, thereby facilitating high‐performance ZIBs is designed. This study delves into the influence of the loading amount and crystal phase of the TiO2 coating layers on separator modification. Zn symmetric cells employing the anatase TiO2‐modified glass fiber (A‐TiO2@GF) separator demonstrate superior Zn2+ ion transport kinetics in a mild ZnSO4 electrolyte, ensuring sustained long‐term stability and uniform Zn deposition. Furthermore, the reduced hydrogen evolution reaction (HER) activity of A‐TiO2 coatings curbs H+ ion migration, minimizing interfacial corrosion and HER. Consequently, the assembled Zn||CaV8O20 zinc‐ion full cells demonstrate outstanding long‐term durability and impressive specific capacity, boasting a discharge capacity of 142 mAh g−1 after 1000 cycles. This work introduces a straightforward interface engineering strategy for creating efficient separators in zinc‐ion batteries, promoting uniform Zn deposition.

Separator pore size induced oriented Zn deposition

Aqueous zinc batteries (AZBs) are promising alternatives to lead-acid batteries for large-scale energy storage. In this work, we developed a TiO2-grafted polyethylene (TiO2-PE) separator for AZBs with excellent hydrophilicity. The TiO2-PE separator demonstrates the thinnest thickness of 9 μm, significantly decreasing the inactive mass of the entire battery comparing with the commercial glass fiber separator (260 μm). We further prove that the separator pore size can modulate the Zn deposition morphology. The (002)-orientated Zn deposition is induced when the pore size is smaller than the crystal critical length. Therefore, the 0.2 μm pores in TiO2-PE induce a (002)-orientated Zn deposition, while the 2 μm pores in glass fiber lead to a randomly oriented growth of Zn metal. This work highlights the opportunities in the pore size-modulated deposition/dissolution process in Zn and other metal batteries.

Unravelling the deposition of Zn and Sn as corrosion inhibitor on aluminum (Al) surface for Al-air battery application with sodium chloride electrolytes

Recently, Aluminum (Al) has been extensively developed as an anode material for Al-air batteries. High corrosion rate and slow kinetic reactions of Al in anode application drive the recent research to coat with other more noble metals. Therefore, the primary objective of this work is identifying the effect of zinc (Zn) and tin (Sn) coating on high purity Al surface for electrochemical properties improvement. The employed method of metal oxide coating was electrodeposition process. The structural and morphological of electrodeposition was investigated by scanning electron microscopy (SEM). The surface of Zn-Al was finer than Sn–Al. Additionally, the observed cracks on the surface were analyzed and interpreted as indicative of mixed metal oxide (MMO) coating behavior. In electrochemical performance, the Zn–Al half-cell exhibits a consistent open circuit potential value of −0.94 V. This value is the most stable compared with other variables. Remarkably, the discharge time that represents full-cell of Zn–Al and N-doped carbon-based cathode performance was about 14 h, which is nearly fourteen orders compared with Al variables that can only sustain in an hour. The electrodeposition also contributes to enhancing the specific capacity from 40.763 m Ah g−1 to become 324.627 mAh g−1. In line with other measurements, the corrosion rate with linear polarization measurement placed Zn–Al with the smallest corrosion rate, that is 3.71 × 10-5 mm/year. All the electrochemical measurements used 3.5 % NaCl as the model of seawater electrolytes. This finding could be a reliable option of aluminum air battery development on larger scale in the future.

Two Birds with One Stone: Green Solvent Enabled High‐Stability and Durable Zn Anode in Both Non‐Aqueous and Aqueous Electrolytes

AbstractRechargeable zinc batteries are promising choices for eco‐friendly, safe and cost‐effective energy storage solutions. However, their commercial adoption faces challenges such as low Coulombic efficiency (CE) and poor reversibility of Zn anodes. To address these issues, a new green electrolyte based on N,N'‐Dimethylpropyleneurea (DMPU) has been developed, affording a robust, dendrite‐free Zn anode with over 5000 h of cycle stability and a high average CE of 98.49%. Zn anode in DMPU‐electrolyte significantly outperforms aqueous electrolyte with 67 times longer cycle life, demonstrating excellent anode stability. Moreover, ultra‐stable Zn anode in DMPU‐electrolyte cycled for over 10 000 cycles at 1.0 mA cm−2 showcases excellent reversibility. The Dimethylpropyleneurea‐triflate anion generated solid electrolyte interphase enables homogeneous and rapid Zn2+‐diffusion at the electrode interface, leading to a structured hexagonal Zn deposit. Furthermore, as electrolyte additive, DMPU significantly stabilizes Zn anode at severe conditions (5.0 and 10.0 mA cm−2) along with remarkable enhancement in CE (99.12%). This study offers valuable insights into the development of hybrid and organic electrolytes to advance Zn battery technology.

Facile Electrolytic (111)‐Textured Copper Foil for Dendrite‐Free Zinc Metal Batteries

AbstractAqueous Zn metal batteries are emerging as a promising candidate for the next‐generation largescale energy storage system due to their high safety, low lost, and eco‐friendliness. Nevertheless, their practical application is restricted by the uncontrollable Zn dendrite growth and the limited utilization of the Zn metal anode. Herein, a room temperature electrodeposition strategy based on an optimized rate relationship between the diffusion and consumption of Cu2+ to prepare a (111)‐textured Cu current collector for the construction of the dendrite‐free Zn metal anode with high reversibility is developed. Attributed to the high lattice match between the (002) facet of Zn with the (111) facet of Cu, the deposition of Zn along its [001] orientation is achieved on the (111)‐textured Cu. The (002) facets horizontally aligned with the current collector endow Zn with the dendrite‐free planar construction and superior corrosion resistance, resulting in a high reversibility with a long life‐span over 2186 cycles. Impressively, the resultant Zn anodes can stabilize the operation of pouch cells with an extremely demanding negative‐to‐positive capacity ratio of 2. This work provides a new avenue for the development of the current collectors for the low‐cost sustainable energy storage.

Arrays of Hierarchical Zincophilic Nanorods with Trapping‐and‐Leveling Deposition for Ultrastable Zn Metal Anodes

AbstractRechargeable aqueous zinc‐ion batteries (ZIBs) are highly promising for large‐scale sustainable energy storage applications, but there remain serious problems such as Zn dendrites and side reactions that limit the cycling performance. Herein, arrays of core–shell nanorods on Cu foam are developed to stabilize zinc anodes, which have a hierarchical topological structure consisting of N‐doped carbon layers embedded with a zincophilic component of Cu5Zn8 alloy (Cu5Zn8@NC). It is found that the inner Cu5Zn8 alloys have minimized nucleation barriers and act as preferred nucleation sites, and the hierarchical arrays provide the protective layers to further accommodate the high‐capacity plating Zn, leading to a trapping‐and‐leveling process of Zn deposition. The as‐obtained Zn layers play an important role in homogenizing the interfacial ionic fluxes and reducing the local current densities. As a result, the optimized Cu5Zn8@NC host yields a superb Coulombic efficiency of 99.7% over 5000 plating/stripping cycles, and the corresponding symmetric cell delivers an ultralong dendrite‐free cycle life of 7000 h with a low overpotential of 16.5 mV at 1 mA cm−2 and 1 mAh cm−2. The ZIB assembled with the zinc anode and a V2O5 cathode exhibits long‐term charging/discharging cycles as well, up to 89.2% capacity retention after 10 000 cycles.