Zinc Dendrite Growth Research Articles

Multi-Channel Engineering of 3D Printed Zincophilic Anodes for Ultrahigh-Capacity and Dendrite-Free Quasi-Solid-State Zinc-Ion Microbatteries.

Zinc-ion microbatteries (ZIMBs) are regarded as one of most promising miniaturized energy storage candidates owing to their high safety, compatible device size, superior energy density, and cost efficiency. Nevertheless, the zinc dendrite growth during charging/discharging and the inflexible device manufacturing approach seriously restrict practical applications of ZIMBs. Herein, we report a unique material extrusion 3D printing approach with reinforced zincophilic anodes for ultrahigh-capacity and dendrite-free quasi-solid-state ZIMBs. A 3D printed N-doped hollow carbon nanotube (3DP-NHC) multichannel host is rationally designed for desirable dendrite-free zinc anodes. Favorable structural metrics of 3DP-NHC hosts with abundant porous channels and high zincophilic active sites enhance the ion diffusion rate and facilitate uniform zinc deposition behavior. Rapid zinc-ion migration is predicted through molecular dynamics, and zinc dendrite growth is significantly suppressed with homogeneous zinc-ion deposition, as observed by in situ optical microscopy. 3D printed symmetric zinc cells exhibit an ultralow polarization potential, a glorious rate performance, and a stable charging/discharging process. Accordingly, 3D printed quasi-solid-state ZIMBs achieve an outstanding device capacity of 11.9 mA h cm-2 at 0.3 mA cm-2 and superior cycling stability. These results reveal a feasible approach to effectively restrain zinc dendrite growth and achieve high performance for state-of-the-art miniaturized energy storage devices.

Numerical simulation of factors in charge of dendrite growth in zinc-nickel single flow batteries

There is a potential danger of battery internal short-circuiting and shortened life span in zinc-nickel single flow batteries which is usually caused by the formation of dendritic crystals as a result of non-uniform electrodeposition. For the purpose of restraining dendrite growth and prolonging the battery service life, it is necessary to investigate the mechanism of dendrite growth that occurs on the surface of zinc anode. Here, a model for two-dimensional zinc dendrite growth is established by the phase field-lattice Boltzmann method (PF-LBM) to simulate how the morphology of zinc dendrites evolves as well as the corresponding distribution of the concentration field, potential field and flow field, and to analyze the influences of the applied voltage, electrolyte flow rate, anisotropy strength and exchange current density on dendrite growth. As the results show, higher exchange current density and applied voltage can promote dendrite growth. By choosing a suitable anisotropic strength, it is possible to change the morphology of the dendrites and decrease the formation of dendrites. Enlarging the electrolyte flow rate may make the distribution of ion concentration more uniform, which can inhibit the dendrite growth as well as affect the morphology of dendrites.

Inert Group-Containing Electrolyte Additive Enabling Stable Aqueous Zinc-Ion Batteries.

Aqueous zinc ion batteries (AZIBs) are considered promising energy storage devices because of their high theoretical energy density and cost-effectiveness. However, the ongoing side reactions and zinc dendrite growth during cycling limit their practical application. Herein, trisodium methylglycine diacetate (Na3MGDA) additive containing the additional inert group methyl is introduced for Zn anode protection, and the contribution of methyl as an inert group to the Zn anode stability is discussed. Experimental results reveal that the methyl group with various effects enhances the interaction between the polar groups in Na3MGDA and the Zn2+/Zn anode. Thus, the polar carboxylate negative ions in MGDA anions can more easily modify the solvation structure and adsorb on the anode surface in situ to establish a hydrophobic electrical double layer (EDL) layer with steric hindrance effects. Such the EDL layer exhibits a robust selectivity for Zn deposition and a significant inhibition of parasitic reactions. Consequently, the Zn||Zn symmetric battery presents 2375h at 1mAcm-2, 1mAhcm-2, and the Zn||V6O13 full battery provides 91% capacity retention after 1300 cycles at 3Ag-1. This study emphasizes the significant role of inert groups of the additive on the interfacial stability during the plating/stripping of high-performance AZIBs.

Diethylene glycol dimethyl ether effectively regulates the electrochemical behavior of zinc anode

A non-proton polar solvent Diethylene glycol dimethyl ether(DGDE) was used as a cosolvent in aqueous electrolyte, the strong binding of O lone pair electrons in the CO bond to Zn2+ enabled DGDE to participate in the first solvent sheath to reconstruct the Zn2+ solvation structure. Meanwhile, the adsorption of DGDE on the surface of zinc electrode and the steric hindrance effect of DGDE molecule induced the horizontal deposition of hexagonal Zn(002) crystal plane, suppressed the zinc dendrite growth, while formed a dense protective layer on the surface of the zinc electrode to avoid it from the corrosion by the electrolyte. The initial CE of Zn‖Cu semi-battery was increased from 77 % with pure ZnSO4 electrolyte to 87 % with 0.1 M DGDE added at 0.5 mA cm−2 and 1 mAh cm−2, and the average CE at 1 mA cm−2 and 1 mAh cm−2 was maintained at 98.7 % during the long cycle. As cycled at 3C (1C = 308mAh g −1) in 0.1 M DGDE electrolyte, Zn‖ε-MnO2 full battery demonstrated much slower discharge decay, after 580 cycles, the capacity retained 138mAh g −1, 3.5 times of the system of 1 M ZnSO4. Adding trace DGDE to aqueous electrolyte can effectively improve CE and inhibit the zinc dendrite growth, not only maintains the low-cost, quick assembly advantages of aqueous zinc-ion battery, but also lays a foundation for its further application.

Achieving stable zinc metal anodes by regulating ion transfer and desolvation behavior

Aqueous Zn ion batteries (AZIBs) are considered to be highly promising rechargeable secondary batteries. However, the growth of zinc dendrites and irreversible side reactions hinder its further application. In this paper, an artificial interfacial protective layer of phenol–formaldehyde resin (PF) was constructed to achieve high-performance zinc anode. There is a strong interaction between hydroxyl groups in PF and Zn ions. This interaction modulates the solvation sheath of Zn ions and promotes the desolvation of [Zn(H2O)6]2+, which reduces the side reactions induced by reactive H2O. Furthermore, the pore structure of PF provides ion-confinement effect to regulate the Zn ions flux, thus reducing the growth of dendrites caused by inhomogeneous deposition. Thus, the PF coating has the dual effect of fast desolvation and ion confinement, which is beneficial to the uniform Zn ions deposition and achieves highly stable zinc anodes. Consequently, the Zn@PF||MnO2 full cell can be stably cycled for 1500 cycles at 1.5 A/g and the capacity retention remains 82.4 %. This method provides a convenient and practical approach to tackle the problems of zinc anodes, and establishes the foundation for their further application.

An Electrochemically Initiated Self-Limiting Hydrogel Electrolyte for Dendrite-Free Zinc Anode.

The zinc dendrite growth generally relies upon a "positive-feedback" mode, where the fast-grown tips receive higher current densities and ion fluxes. In this study, a self-limiting polyacrylamide (PAM)hydrogel that presents negative feedback to dendrite growth is developed. The monomers are purposefully polymerized at the dendrite tips, then the hydrogel reduces the local current density and ion flux by limiting zinc ion diffusion with abundant functional groups. As a consequence, the accumulation at the dendrite tips is restricted, and the (002) facets-oriented deposition is achieved. Moreover, the refined porous structure of the gel enhances Coulombic Efficiency by reducing water activity. Due to the synergistic effects, the zinc anodes perform an ultralong lifetime of 5100h at 0.5mAcm-2 and 1500h at 5mAcm-2, which are among the best records for PAM-based gel electrolytes. Further, the hydrogel significantly prolongs the lifespan of zinc-ion batteries and capacitors by dozens of times. The developed in situ hydrogel presents a feasible and cost-effective way to commercialize zinc anodes and provides inspiration for future research on dendrite suppression using the negative-feedback mechanism.

Two Birds with One Stone: V4 C3 MXene Synergistically Promoted VS2 Cathode and Zinc Anode for High-Performance Aqueous Zinc-Ion Batteries.

Aqueous zinc-ion batteries (AZIBs) are considered to be a rising star in the large-scale energy storage area because of their low cost and environmental friendliness properties. However, the limited electrochemical performance of thecathode and severe zinc dendrite of the anode severely hinder the practical application of AZIBs. Herein, a novel 3D interconnected VS2 ⊥V4 C3 Tx heterostructure material is prepared via one-step solvothermal method. Morphological and structural characterizations show that VS2 nanosheets are uniformly and dispersedly distributed on the surface of theV4 C3 MXene substrate, which can effectively suppress volume change of the VS2 . Owing to the open heterostructure along with the high conductivity of V4 C3 MXene, the VS2 ⊥V4 C3 Tx cathode shows a high specific capacity of 273.9mAhg-1 at 1Ag-1 and an excellent rate capability of 143.2mAhg-1 at 20Ag-1 . The V4 C3 MXene can also effectively suppress zinc dendrite growth when used as protective layer for the Zn anode, making the V4 C3 Tx @Zn symmetric cell with a stable voltage profile for ≈1700h. Benefitting from the synergistic modification effect of V4 C3 MXene on both the cathode and anode, the VS2 ⊥V4 C3 Tx ||V4 C3 Tx @Zn battery exhibits a long cycling lifespan of 5000 cycles with a capacity of 157.1mAhg-1 at 5Ag-1 .

Effect of Na2SiO3 and TEA Electrolyte Additives on the Corrosion Inhibition of Zinc Electrodes and Electrochemical Performance of Rechargeable Alkaline Manganese Batteries

To inhibit hydrogen evolution corrosion, passivation, and zinc dendrite growth during the charging and discharging of the zinc negative electrode of rechargeable alkaline manganese battery containing ultra-fine zinc powders, the effects of the single addition amounts of inorganic corrosion inhibitor Na2SiO3 and organic corrosion inhibitor TEA and their compounding ratio on the corrosion inhibition effect and the charging and discharging performance of alkaline manganese battery were systematically investigated in this paper. SEM and XPS were used to observe the microscopic morphology of the zinc anode, and the inhibition mechanisms of the relevant inhibitors were explored. The results show that, the addition of Na2SiO3 and TEA can synergistically improve the coverage of the protective film, thereby inhibiting hydrogen evolution corrosion, passivation and dendrites of zinc electrodes. Compared to blank electrolyte, when the composite concentration of Na2SiO3 and TEA is 1 g l−1 Na2SiO3+56.25 mg l−1 TEA, the hydrogen evolution corrosion inhibition efficiency can reach 70.56%, the initial specific capacity and the specific capacity after 50 cycles can increase from 160.7 mAh g−1, 58 mAh g−1 to 198.4 mAh g−1, 74 mAh g−1, respectively. This study has great theoretical and engineering value for guiding the design of electrolytes for rechargeable alkaline manganese batteries.

Phosphorous‐Doping Strategy Enabled “Concrete‐Slab”‐Like Zn Layer for Highly Stable 3D Composite Anode

AbstractZinc electroplating/stripping is a promising electrochemical reaction for aqueous battery anodes, offering advantages such as high safety, low cost, and fast reaction kinetics. However, the growth of zinc dendrites is a major obstacle impeding its commercialization. To address these challenges, a phosphorus‐doping strategy is proposed for preparing a high Zn‐affinity C3N4 coupled carbon nanotube 3D framework (PCN‐S). The addition of P facilitates the efficient crystallization of Zn that leads to the formation of a “concrete‐slab”‐like zinc layer on the PCN‐S surface. Moreover, the unique “release effect” possessed by the P‐doped 3D framework contributes to more stable cycling at high current. Such structural characteristics result in significantly enhanced stability of Zn metal deposition and extend the cycle life of full cells. The Zn@PCN‐S//Zn@PCN‐S symmetric cell exhibits an impressive long‐term cycle time exceeding 1500 h (1 mA cm‒2). Consequently, aqueous rechargeable zinc‐metal batteries constructed with the 3D Zn@PCN‐S anode can achieve a specific energy of approximately ≈340 mAh g‒1 and cycling for over 600 h. This work introduces a promising option for next‐generation energy storage technologies.

A Functional Janus Ag Nanowires/Bacterial Cellulose Separator for High-Performance Dendrite-Free Zinc Anode Under Harsh Conditions.

Aqueous zinc-ion batteries (AZIBs) offer promising prospects for large-scale energy storage due to their inherent abundance and safety features. However, the growth of zinc dendrites remains a primary obstacle to the practical industrialization of AZIBs, especially under harsh conditions of high current densities and elevated temperatures. To address this issue, a Janus separator with an exceptionally ultrathin thickness of 29µm is developed. This Janus separator features the bacterial cellulose (BC) layer on one side and Ag nanowires/bacterial cellulose (AgNWs/BC) layer on the other side. High zincophilic property and excellent electric/thermal conductivity of AgNWs make them ideal for serving as an ion pump to accelerate Zn2+ transport in the electrolyte, resulting in greatly improved Zn2+ conductivity, deposition of homogeneous Zn nuclei, and dendrite-free Zn. Consequently, the Zn||Zn symmetrical cells with the Janus separator exhibit a stable cycle life of over 1000 h under 80mA cm-2 and are sustained for over 600 h at 10mA cm-2 under 50 °C. Further, the Janus separator enables excellent cycling stability in AZIBs, aqueous zinc-ion capacitors (AZICs), and scaled-up flexible soft-packaged batteries. This study demonstrates the potential of functional separators in promoting the application of aqueous zinc batteries, particularly under harsh conditions.

Advancements in the Exploration of Gel Electrolytes for Aqueous Zinc Ion Batteries

Aqueous zinc-ion batteries (ZIBs) are seen as a superior substitute for lithium-ion batteries (LIBs) due to their excellent safety, low cost, and eco-friendliness. However, problems such as zinc dendrite growth, hydrogen evolution reaction and electrode corrosion hinder the commercialization of batteries. Electrolyte as a link to other parts of the battery, has been widely concerned. Hydrogel is a kind of cross-linked product filled with water, which has the advantages of high theoretical capacity, good flexibility, good water retention and good mechanical properties, and becomes a potential candidate for ZIBs. By summarizing the development of hydrogel electrolytes, the cross-linking types of gel electrolytes and their applications in ZIBs were reviewed in this paper. Finally, the application of gel electrolyte in ZIBs is summarized and prospected, which brings a meaningful reference for the development of ZIBs. Copyright © 2023 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

Inhibition of zinc dendrite growth in zinc-air batteries by alloying the anode with Ce and Yb

Zinc-air batteries have garnered significant attention owing to their high energy density and substantial anode active substance storage. Despite their potential advantages, the application of zinc-air batteries has been hindered in various domains by rapid performance degradation and reduced service life caused by zinc dendrite growth during cycling. This study presents a method of alloying zinc anodes with rare earth metals, such as Ce and Yb, as well as alkaline earth metal Mg to mitigate the growth of zinc dendrites. This is achieved by altering the anisotropy modulus and intensity at the interface energy of the zinc anode. This approach was verified using a COMSOL phase-field model based on an experimental study. The findings demonstrate that the optimal suppression of zinc dendrite growth was achieved with the anisotropy modulus of 6 and the inhibition efficiency is 35%. Moreover, the degree of anisotropic intensity exhibited by the interfacial energy was inversely proportional to the inhibition of zinc dendrite growth. The most effective approach to inhibit dendrite growth involved using a zinc anode composition of 98% Zn–2% Mg and 93.5% Zn–6.5% Yb. The addition of Ce into the zinc anode was found to increase the anisotropy modulus of the anode interface energy, changing the direction and decreasing the height of zinc dendrite growth. Similarly, the addition of Yb to the zinc anode decreased the anisotropic intensity of the interface energy, thereby impeding the growth of the main stem dendrite.

Stable Solid‐State Zinc–Iodine Batteries Enabled by an Inorganic ZnPS3 Solid Electrolyte with Interconnected Zn2+ Migration Channels

AbstractAqueous zinc–iodine (Zn–I2) batteries, with their outstanding merits in safety, cost, and environmental friendliness, have received extensive attention. However, the unstable electrochemistry at the electrode–electrolyte interface originating from free water results in zinc dendrite growth, hydrogen evolution reaction (HER), and polyiodide ions shuttle, hindering their practical applications. Herein, solid‐state Zn–I2 batteries based on an inorganic ZnPS3 (ZPS) electrolyte are developed to overcome inherent interfacial issues associated with aqueous electrolytes. The inorganic ZnPS3 electrolyte, with a low Zn2+ diffusion energy barrier of ≈0.3 eV, demonstrates an exceptional ion conductivity of 2.0 × 10−3 S cm−1 (30 °C), which also satisfies high chemical/electrochemical stability and mechanical strength. The solid Zn2+ conduction mechanism, facilitated by bounded water only on grains, effectively suppresses HER and polyiodide ions shuttling. During cycling, a ZnS functional layer is spontaneously formed on the anode/electrolyte interphase, promoting dendrite‐free Zn deposition behavior with a more stable (002) crystal orientation. Consequently, the solid‐state configuration of Zn–I2 battery enables an impressive reversible capacity of 154.2 mAh g−1 after 400 cycles at 0.1 A g−1. Importantly, the compatibility of the solid‐state ZnPS3 electrolyte is also confirmed in the Zn||CuS cell, indicating its potential as a versatile platform for developing inorganic solid‐state zinc‐ion batteries (ZIBs).

Pivotal Role of Organic Materials in Aqueous Zinc‐Based Batteries: Regulating Cathode, Anode, Electrolyte, and Separator

AbstractAqueous zinc‐based batteries have garnered considerable interest as promising energy storage devices due to the low cost, remarkable energy density, high safety, and eco‐friendliness. However, the mutual challenges of cathode dissolution, electrolyte parasitic reactions, disordered zinc dendrite growth, and easily punctured separator have significantly impeded the widespread commercialization of aqueous zinc‐based batteries. Realizing high‐performance zinc‐based batteries becomes imperative yet remains extremely challenging. To address these concerns, great efforts have recently been made to design high‐performance zinc‐based batteries. Here the state‐of‐the‐art in organic materials is critically reviewed for aqueous zinc‐based batteries, covering main components of a battery. This review provides a comprehensive overview on the design strategies of organic materials for zinc‐based batteries, encompassing cathode, anode, electrolyte, and separator. Furthermore, the challenges and prospective research directions are also discussed to provide a guideline for further development of highly stable zinc‐based batteries.

Building Ion-Conductive Supramolecular Elastomeric Protective Layer via Dynamic Hard Domain Design for Stable Zinc Metal Anodes.

The instability of zinc metal anode caused by zinc dendrite growth and severe parasitic reactions has significantly restricted the extensive application of rechargeable aqueous zinc-ion batteries (RAZBs). Herein, based on the strategy of dynamic hard domains, we develop an ion-conductive supramolecular elastomer consisting of Zn salts and the polyurethane-urea-polypropylene glycol polymer skeleton. This elastomer combines high mechanical strength, high ionic conductivity, decent hydrophobicity, and high adhesion to stabilize the electrode-electrolyte interface. In the elastomer system, this elastomer can dynamically adapt to the volume changes of Zn anodes during repeated zinc plating/stripping processes through the reversible dissociation/reassociation of hierarchical hydrogen bonds (H-bonds) formed by the polar groups of urea and urethane moieties. Meanwhile, the coordination of Zn2+ with soft polypropylene glycol (PPG) segments contributes to fast ion transport. This hydrophobic elastomer can also effectively inhibit water-induced corrosion by shielding the active Zn metal from the aqueous electrolyte. Based on the above synergies, the surface-modified anode shows excellent cycling stability above 550 h at a high current density of 5 mA cm-2 and a capacity of 2.5 mAh cm-2. Moreover, the assembled Zn//MnO2 full cell also displayed an enhanced electrochemical performance. This work provides inspiration for the design of solid electrolyte interphase (SEI) layers in aqueous battery chemistry to accelerate the application of RAZBs.

Inhibition of Zinc Dendrite Growth by WC-Cellulose Separators for High-Performance Zinc-Ion Batteries

Inhibition of Zinc Dendrite Growth by WC-Cellulose Separators for High-Performance Zinc-Ion Batteries

The Organic Ligand Etching Method for Constructing In Situ Terraced Protective Layer Toward Stable Aqueous Zn Anode.

The stability of aqueous Zn-ion batteries (AZIBs) is highly dependent on the reversibility of stripping/plating Zn anode. In this work, an organic ligand etching method is proposed to develop a series of in situ multifunctional protective layers on Zn anode. Particularly, the 0.02m [Fe(CN) 6]3- etching solutions can spontaneously etch the Zn anode, creating an in situ protective layer with unique terraced structure, which blocks the direct contact between the electrode and electrolyte and increases the area for Zn2+ ions deposition. Interestingly, all elements in the organic ligands (i.e., C, N, Zn, and Fe) exhibit strong zincophilic, significantly promoting zinc deposition kinetics and enhancing 3D nucleation behavior to inhibit zinc dendrite growth. As a result, the etched Zn anode can provide as high a Coulombic efficiency of 99.6% over 1000 cycles and sustain over 400 h long-term stability at a high current density of 10mA cm-2 . As general validation, the small amount of metal cations additives (e.g., Ni2+ , Mn2+ , and Cu2+ ) can accelerate the synthesis of artificial interface layers with 3D structures and also regulate zinc deposition behavior. This work provides a new idea from the perspective of etching solution selection for surface modification of Zn metal anode.

Comprehensive Review of Electrolyte Modification Strategies for Stabilizing Zn Metal Anodes

AbstractIn response to the need of sustainable development, there is an increasing demand for electrical energy storage, leading to a stimulated pursuit of advanced batteries. Aqueous zinc ion batteries (AZIBs) have attracted much attention due to their low cost, high safety, and environmental friendliness. Despite the great efforts made by researchers in designing and developing high‐performance AZIBs, several challenges remain. Particularly for Zn anode, the growth of zinc dendrites and occurance of various side reactions significantly hinder the advancement of AZIBs. This review article aims to discuss the principles of AZIBs, the electrolyte's structure and properties, the challenges faced by AZIBs anodesm and the strategies to improve battery performance through electrolyte modification in a systematic manner. In conclusion, potential future directions aimed at enhancing the stability of zinc anodes and cathodes by electrolyte modification strategies are proposed to ensure that research efforts are geared toward achieving realistic performance targets for commercializing AZIBs.

An aqueous electrolyte densified by perovskite SrTiO3 enabling high-voltage zinc-ion batteries

The conventional weak acidic electrolyte for aqueous zinc-ion batteries breeds many challenges, such as undesirable side reactions, and inhomogeneous zinc dendrite growth, leading to low Coulombic efficiency, low specific capacity, and poor cycle stability. Here, an aqueous densified electrolyte, namely, a conventional aqueous electrolyte with addition of perovskite SrTiO3 powder, is developed to achieve high-performance aqueous zinc-ion batteries. The densified electrolyte demonstrates unique properties of reducing water molecule activity, improving Zn2+ transference number, and inducing homogeneous and preferential deposition of Zn (002). As a result, the densified electrolyte exhibits an ultra-long cycle stability over 1000 cycles in Zn/Ti half cells. In addition, the densified electrolyte enables Zn/MnO2 cells with a high specific capacity of 328.2 mAh g−1 at 1 A g−1 after 500 cycles under an extended voltage range. This work provides a simple strategy to induce dendrite-free deposition characteristics and high performance in high-voltage aqueous zinc-ion batteries.

A review on covalent organic frameworks for rechargeable zinc-ion batteries

In recent years, rechargeable zinc-ion batteries (ZIBs) are considered to be a promising alternative to lithium-ion batteries owing to their high safety and theoretical capacity with low cost. Nevertheless, the in-depth development of rechargeable zinc-ion batteries is restricted by a sequence of issues, such as the dissolution and structure collapse of cathode materials, the formation of by-products, severe anode corrosion, passivation, and the growth of zinc dendrites. The covalent organic frameworks (COFs) can solve the above problems to a certain extent owing to their ideal characteristics, such as rigid structure, insolubility, high porosity, and abundant active sites. COFs, as advanced materials for ZIBs, have attracted researchers’ attention. In this review, we systematically summarized the synthesis methods of COFs and discussed the application of several advanced characterization technologies in COFs, which would provide a reference for the in-depth research of COFs. In addition, we elucidated the use of COFs as cathode materials and anode protective layers in rechargeable ZIBs. Finally, we discussed the challenges and solutions in the development of COF materials, which would provide constructive insights into the future direction of COFs.