RESUMO
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.
RESUMO
The efficient utilization of the metallic Zn in rechargeable aqueous Zn-ion batteries (RAZBs) struggle to suffer from parasitic Zn dendrite formation, hydrogen evolution reactions as well as severe interfacial degradation at high areal capacity loadings. This study thus proposes to employ the modified crown ether as an aqueous electrolyte additive to regulate the Zn2+ desolvation kinetic and facilitates the horizontally oriented (002) deposition of Zn, extending the lifespan of both the symmetric cell and full cell models. Specifically, zincophilic cyano and hydrophobic selenium atoms are incorporated into the crown ether supramolecule to enhance Zn2+ coordination and desolvation capability. The addition of 4-cyanobenzo-21-crown-7-selenium at a low concentration of 0.5 wt.% effectively mitigates hydrogen evolution and Zn corrosion caused by water, promoting the oriented deposition of Zn2+. The Zn||V2O5 full cell prototype, assembled with the areal capacity loadings of 2 mAh cm-2 and N/P ratio of 2.95, exhibits negligible capacity fading at 2.0A g-1 for 300 cycles, highlighting the commercial feasibility of supramolecular macrocycles additive for practical RAZBs applications.
RESUMO
Zinc metal anodes encounter significant challenges, including dendrite growth, hydrogen evolution, and corrosion, all of which impede the rate capability and longevity of aqueous zinc-ion batteries (AZIBs). To effectively tackle these issues, we introduced Tween-80 into the traditional ZnSO4 electrolyte as an additive. Tween-80 possesses electronegative oxygen atoms that enable it to adsorb onto the zinc (Zn) anode surface, facilitating the directional deposition of Zn metal along the (002) orientation. The hydroxyl and ether groups within Tween-80 can displace some of the coordinated water molecules in the Zn2+ inner solvation shell. This disruption of the hydrogen bond network regulates the solvation structure of Zn2+ ions and suppresses the possibility of hydrogen evolution. Moreover, the long hydrocarbon chain present in Tween-80 exhibits excellent hydrophobic properties, aiding in the resistance against corrosion of the Zn anode by water molecules and reducing hydrogen evolution. Consequently, a symmetric cell equipped with the Tween-80 additive can cycle stably for over 4000 h at 1 mA cm-2 and 1 mA h cm-2. When paired with the V2O5 cathode, the full cell demonstrates a high-capacity retention rate exceeding 80 % over 1000 cycles at a current density of 2 A g-1. This study underscores the advantages of utilizing non-ionic surfactants for achieving high-performance aqueous zinc-ion batteries.
RESUMO
Dendrite growth of lithium (Li) metal anodes is considered as one of the most tough issues for Li metal batteries with a theoretically high energy density. This is attributed to the rapid exhaustion of Li ions at the electrode/electrolyte interface, which is even worse at low temperatures with poor diffusion kinetics of Li ions. Here, pulse charge with intermittent rest time during battery charging is proposed to handle the dendrite growth issue of Li metal anodes at low temperatures. The depleted Li ions near the interfaces can be rapidly replenished during the rest time, thus effectively suppressing the dendrites growth. Further investigations indicate that the large dendrites can be suppressed at the Li ion nucleation stage. The equivalent lifespan considering the rest time is proposed. At -10oC, the lifespan of Li||Li batteries cycled under 3 mA cm-2 and 1 mAh cm-2 is increased from 24 h to equivalent 64 h. Li ||LiNi0.5Co0.2Mn0.3O2 batteries with 80% capacity retention can be stably operated from 39 cycles to 56 cycles. This design presents an efficient and convenient strategy to regulate the deposition behaviors of Li metal anodes with a dendrite-free morphology.
RESUMO
Electrolyte additive engineering is a crucial method for enhancing the performance of aqueous zinc-ion batteries (AZIBs). Recently, most research predominantly focuses on the role of functional groups in regulating electrolytes, often overlooking the impact of molecule stereoscopic configuration. Herein, two isomeric sugar alcohols, mannitol and sorbitol, are employed as electrolyte additives to investigate the impact of the stereoscopic configuration of additives on the ZnSO4 electrolyte. Experimental analysis and theoretical calculations reveal that the primary factor for improving Zn anode performance is the regulation of the solvation sheath by these additives. Among the isomers, mannitol exhibits stronger binding energies with Zn2+ ions and water molecules due to its more suitable stereoscopic configuration. These enhanced bindings allow mannitol to coordinate with Zn2+, contributing to solvation structure formation and reducing the active H2O molecules in the bulk electrolyte, resulting in suppressed parasitic reactions and inhibited dendritic growth. As a result, the zinc electrodes in mannitol-modified electrolyte exhibit excellent cycling stability of 1600 h at 1 mA cm-2 and 900 h at 10 mA cm-2, respectively. Hence, this study provides novel insights into the importance of suitable stereoscopic molecule configurations in the design of electrolyte additives for highly reversible and high-rate Zn anodes.
RESUMO
The inevitable shuttling and slow redox kinetics of lithium polysulfides (LiPSs) as well as the uncontrolled growth of Li dendrites have strongly limited the practical applications of lithium-sulfur batteries (LSBs). To address these issues, we have innovatively constructed the carbon nanotubes (CNTs) encapsulated Co nanoparticles in situ grown on TiN-MXene nanosheets, denoted as TiN-MXene-Co@CNTs, which could serve simultaneously as both sulfur/Li host to kill "three birds with one stone" to (1) efficiently capture soluble LiPSs and expedite their redox conversion, (2) accelerate nucleation/decomposition of solid Li2S, and (3) induce homogeneous Li deposition. Benefiting from the synergistic effects, the TiN-MXene-Co@CNTs/S cathode with a sulfur loading of 2.5â mg cm-2 could show a high reversible specific capacity of 1129.1â mAh g-1 after 100 cycles at 0.1â C, and ultralong cycle life over 1000 cycles at 1.0â C. More importantly, it even achieves a high areal capacity of 6.3â mAh cm-2 after 50 cycles under a sulfur loading as high as 8.9â mg cm-2 and a low E/S ratio of 5.0â µL mg-1. Besides, TiN-MXene-Co@CNTs as Li host could deliver a stable Li plating/striping behavior over 1000â h.
RESUMO
Zinc metal is recognized as the most promising anode for aqueous energy storage but suffers from severe dendrite growth and poor reversibility. However, the coulombic efficiency lacks specificity for zinc dendrite growth, particularly in Zn||Zn symmetric cells. Herein, a novel indicator (fD) based on the characteristic crystallization peaks is proposed to evaluate the growth and distribution of zinc dendrites. As a proof of concept, triethylenetetramine (TETA) is adopted as an electrolyte additive to manipulate the zinc flux for uniform deposition, with a corroborating low fD value. A highly durable zinc symmetric cell is achieved, lasting over 2500 h at 10 mA cm-2 and 400 h at a large discharge of depth (10 mA cm-2, 10 mAh cm-2). Supported by the low fD value, the Zn||TETA-ZnSO4||MnO2 batteries overcome the sudden short circuit and fast capacity fading. The study provides a feasible method to evaluate zinc dendrites and sheds light on the design of highly reversible zinc anodes.
RESUMO
Ammonium chloride (NH4Cl) has been extensively studied as a transparent analogue for investigating the solidification of metals due to its distinctive properties and the simplicity of the experimentation. Furthermore, NH4Cl exhibits a striking resemblance in solidification behavior to the majority of binary eutectic alloy systems, rendering it a valuable model for studying phase transition phenomena. Experiments conducted on ammonium chloride are frequently employed to validate numerical models for predicting grain structures, macrosegregation, and the columnar-to-equiaxed transition (CET). This latter phenomenon arises due to differences in the velocities of columnar dendrite tips and the liquidus isosurface. However, the kinetics of dendrite tip growth, as a function of supersaturation, remains poorly understood for this commonly used alloy. The objective of this study was to utilize the available experimental data in conjunction with Ivantsov correlations to shed light on the ambiguous kinetics. The results indicate that when considering the crystal-melt density ratio, the Ivantsov solution offers a good correlation. Furthermore, incorporating a moderate interfacial kinetic coefficient enhances the correlations further. This correlation can be implemented in numerical models, which will aid in the determination of the columnar front, the columnar-to-equiaxed transition, and the equiaxed growth velocities.
RESUMO
Lithium-sulfur batteries (LSBs) have recently gained extensive attention due to their high energy density, low cost, and environmental friendliness. However, serious shuttle effect and uncontrolled growth of lithium dendrites restrict them from further commercial applications. As "the third electrode", functional separators are of equal significance as both anodes and cathodes in LSBs. The challenges mentioned above are effectively addressed with rational design and optimization in separators, thereby enhancing their reversible capacities and cycle stability. The review discusses the status/operation mechanism of functional separators, then primarily focuses on recent research progress in versatile separators with purposeful modifications for LSBs, and summarizes the methods and characteristics of separator modification, including heterojunction engineering, single atoms, quantum dots, and defect engineering. From the perspective of the anodes, distinct methods to inhibit the growth of lithium dendrites by modifying the separator are discussed. Modifying the separators with flame retardant materials or choosing a solid electrolyte is expected to improve the safety of LSBs. Besides, in-situ techniques and theoretical simulation calculations are proposed to advance LSBs. Finally, future challenges and prospects of separator modifications for next-generation LSBs are highlighted. We believe that the review will be enormously essential to the practical development of advanced LSBs.
RESUMO
Zinc metal anodes in aqueous electrolytes commonly face challenges such as dendrite growth and undesirable side reactions, limiting their application in the field of aqueous zinc-ion batteries (AZIBs) for energy storage. Drawing inspiration from industrial practices involving molybdenum salt solutions for metal modification, a polyoxometalate solution was formulated as a passivation solution for zinc anodes (referred to as MO solution). The formed passivation layer, referred to as the MO layer, exhibited a uniform and protective nature with a thickness of approximately 10 µm. The experimental results demonstrated that this passivation layer effectively suppressed side reactions at the zinc anode interface, as evidenced by lower corrosion current density for MO-Zn anodes. Additionally, the newly plated Zn was uniformly deposited atop the MO layer, ensuring coating integrity and inhibiting dendrite growth. As a result, under more demanding conditions such as a larger current of 8 mA cm-2, the MO-Zn anode displayed an extended cycle life exceeding 420 h in a symmetric battery, with an overpotential as low as 98 mV. This performance significantly outperformed that of commercially available pure Zn foils (with a cycle life of 60 h and an overpotential of 192 mV). Notably, a self-made Na-doped V2O5 served as the cathode (referred to as NaVO), forming the MO-Zn//NaVO full battery. Even under high current test conditions of 2 A/g, the specific capacity of the MO-Zn//NaVO full battery remained substantial at 152.83 mAh/g after 1000 cycles. Furthermore, pouch batteries assembled with NaVO//MO-Zn successfully illuminated small bulbs. This study offers a viable optimization strategy for AZIB anodes and demonstrates the potential of using polyoxometalate solution for etching zinc anodes to inhibit dendrite growth and interfacial corrosion of zinc metal anodes.
RESUMO
The control of the solidification structure of a casting billet is directly correlated with the quality of steel. Variations in superheat can influence the transition from columnar crystals to equiaxed crystals during the solidification process, subsequently impacting the final solidification structure of the billet. In this study, a model of microstructure evolution during billet solidification was established by combining simulation and experiment, and the dendrite growth microstructure evolution during billet solidification under different superheat was studied. The results show that when the superheat is 60 K, the complete solidification time of the casting billet from the end of the 50 mm section is 252 s, when the superheat is 40 K, the complete solidification time of the casting billet is 250 s, and when the superheat is 20 K, the complete solidification time of the casting billet is 245 s. When the superheat is 20 K, the proportion of the equiaxed crystal region is higher-the highest value is 53.35%-and the average grain radius is 0.84556 mm. The proportion of the equiaxed crystal region decreases with the increase of superheat. When the superheat is 60 K, the proportion of the equiaxed crystal region is the lowest-the lowest value is 46.27%-and the average grain radius is 1.07653 mm. Proper reduction of superheat can obviously reduce the size of equiaxed crystal, expand the area of equiaxed crystal and improve the quality of casting billet.
RESUMO
With the in-depth study of solid-state batteries (SSBs), various in situ and ex situ characterization technologies have been widely used to study them. The performance and reliability of SSBs are limited by the formation and evolution of lithium dendrites at the interfaces between solid electrodes and solid electrolytes. We propose a new method based on optical coherence tomography (OCT) for in situ characterization of the internal state of solid-state batteries. OCT is a low-loss, high-resolution, non-invasive imaging technique that can provide real-time monitoring of cross-sectional images of internal structures of SSBs. The morphology, growth, and evolution of lithium dendrites at different stages of cycling under various conditions can be visualized and quantified by OCT. Furthermore, we validate and correlate the OCT results with scanning electron microscopy (SEM) and XPS, proving the accuracy and effectiveness of the OCT characterization method. We reveal the interfacial phenomena and challenges in SSBs and demonstrate the feasibility and advantages of OCT as a powerful tool for in situ and operando imaging of battery interfaces. This study provides new insights into the mechanisms and factors that affect SSB performance, safety, and lifetime, and suggests possible solutions for improvement and application in the field of applied energy.
RESUMO
Dendrite growth and other side-reaction problems of zinc anodes in aqueous zinc-ion batteries heavily affect their cycling lifespan and Coulombic efficiency, which can be effectively alleviated by the application of polymer-based functional protection layer on the anode. However, the utilization rate of functional groups is difficult to improve without destroying the polymer chain. Here, a simple and well-established strategy is proposed by controlling the orientation of functional groups (âSO3H) to assist the optimization of zinc anodes. Depending on the electrostatic effect, the surface-enriched âSO3H groups increase the ionic conductivity and homogenize the Zn2+ flux while inhibiting anionic permeation. This approach avoids the destruction of the polymer backbone by over-sulfonation and amplifies the effect of functional groups. Therefore, the modified sulfonated polyether ether ketone (H-SPEEK) coating-optimized zinc anode is capable of longtime stable zinc plating/stripping, and moreover an enhanced cycling steadiness under high current densities is also detected in a series of Zn batteries with different cathode materials, which achieved by the inclusion of H-SPEEK coating without causing any harmful effects on the electrolyte and cathode. This work provides an easy and efficient approach to further optimize the plating/stripping of cations on metal electrodes, and sheds lights on the scale-up of high-performance aqueous zinc-ion battery technology.
RESUMO
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.
RESUMO
Severe dendrite growth on Zn anodes poses a significant challenge to the development of Zn-based batteries. An effective strategy for inhibiting the formation of Zn dendrites involves electrode modification. In this study, hollow nitrogen-doped carbon spheres (HNCS) are synthesized and used as electrodes to regulate Zn deposition in Zn-based flow batteries. The electrochemical performance of HNCS reveals that the pyrrole nitrogen of HNCS changes the electrode surface state. Therefore, HNCS can inhibit the hydrogen evolution reaction and achieve uniform Zn deposition. HNCS can effectively inhibit dendrite growth and improve the reversibility of the Zn plating/stripping process to regulate the reversibility of Zn-based batteries. The zinc-bromine redox flow battery assembled with HNCS significantly reduces the hydrogen evolution reaction and exhibits a coulombic efficiency of 90 % and energy efficiency of 73 % at a current density of 60â mA cm-2. Similarly, an alkaline zinc-iron flow battery can maintain high Coulombic efficiency and energy efficiency of 83 %.
RESUMO
Aqueous zinc ion batteries (AZIBs) have emerged as a promising battery technology due to their excellent safety, high capacity, low cost, and eco-friendliness. However, the cycle life of AZIBs is limited by severe side reactions and zinc dendrite growth on the zinc electrode surface, hindering large-scale application. Here, an electrolyte optimization strategy utilizing the simplest dipeptide glycylglycine (Gly-Gly) additive is first proposed. Theoretical calculations and spectral analysis revealed that, due to the strong interaction between the amino group and Zn atoms, Gly-Gly preferentially adsorbs on zinc's surface, constructing a stable and adaptive interfacial layer that inhibits zinc side reactions and dendrite growth. Furthermore, Gly-Gly can regulate zinc ion solvation, leading to a deposition mode shift from dendritic to lamellar and limiting two-dimensional dendrite diffusion. The symmetric cell with the addition of a 20 g/L Gly-Gly additive exhibits a cycle life of up to 1100 h. Under a high current density of 10 mA cm-2, a cycle life of 750 cycles further demonstrates the reliable adaptability of the interfacial layer. This work highlights the potential of Gly-Gly as a promising solution for improving the performance of AZIBs.
RESUMO
Aqueous zinc-ion batteries (AZIBs) have gained significant attentions for their inherent safety and cost-effectiveness. However, challenges, such as dendrite growth and anodic corrosion at the Zn anode, hinder their commercial viability. In this paper, an organic-inorganic coating layer (Nafion-TiO2) was introduced to protect the Zn anode and electrolyte interface. Briefly, Nafion effectively shields against the corrosion from water molecules through the hydrophobic wall of -CF3 and guided zinc deposition from the -SO3 functional group, while TiO2 particles with a higher Young's modulus (151 GPa vs 120 GPa from Zn metal) suppress the zinc dendrite formation. As a result, with the protection of Nafion-TiO2, the symmetrical Znâ¥Zn battery shows an improved cycle life of 1,750 h at 0.5 mA cm-2, and the full cell based on Znâ¥MnO2 shows a long cycle life over 1,500 cycles at 1 A g-1. Our research offers a novel approach for protecting zinc metal anodes, potentially applicable to other metal anodes such as those in lithium and sodium batteries.
RESUMO
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 5100 h at 0.5 mA cm-2 and 1500 h at 5 mA cm-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.
RESUMO
Zinc-bromine batteries (ZBBs) have recently gained significant attention as inexpensive and safer alternatives to potentially flammable lithium-ion batteries. Zn metal is relatively stable in aqueous electrolytes, making ZBBs safer and easier to handle. However, Zn metal anodes are still affected by several issues, including dendrite growth, Zn dissolution, and the crossover of Br species from cathodes to corrode anodes, resulting in self-discharge and fast performance fading. Similarly, Br2 undergoes sluggish redox reactions on cathodes, which brings several issues such as poor reaction kinetics, the highly corrosive nature of Br species leading to corrosion of separators and poisoning of anodes, and the volatile nature of Br species causing increased internal pressures, etc. These issues are compounded in flowless ZBB configuration as no fresh electrolyte is available to provide extra/fresh reaction species. In this review, the factors controlling the performance of ZBBs in flow and flowless configurations are thoroughly reviewed, along with the status of ZBBs in the commercial sector. The review also summarizes various novel methodologies to mitigate these challenges and presents research areas for future studies. In summary, this review will offer a perspective on the historical evolution, recent advancements, and prospects of ZBBs.
RESUMO
Novel structural designs for metal organic frameworks (MOFs) are expected to improve ion-transport behavior in composite solid electrolytes. Herein, upper-dimensional MIL-53(Al) nanofibers (MNFs, MIL-53 belongs to the MIL (Material Institute Lavoisier) group) with flower-like nanoflake structures have been designed and constructed via modified hydrothermal coordination. The optimized MNFs with high surface area and porosity can form abundant interfaces with poly(ethylene oxide) (PEO) matrix. The plasticization of MNFs to the PEO matrix will facilitate segmental movement of PEO chains to facilitate Li+ conduction. The unsaturated open metal centers of MNFs can effectively capture bis(trifluoromethanesulfonyl)imide anions (TFSI-) to deliver more free lithium ions for transfer. Moreover, the upper-dimensional nanofiber structure endows lithium ions with a long-range and consecutive transport pathway. The obtained composite solid electrolyte (MNFs@PEO) presents a high ionic conductivity of 4.1 × 10-4 S cm-1 and a great Li+ transference number of 0.4 at 60 °C. The electrolyte also exhibits a stable Li plating/stripping behavior over 1000 h at 0.1 mA cm-1 with inhibited Li dendrite growth. Furthermore, the Li/LiFePO4 and Li/LiNi0.8Mn0.1Co0.1O2 batteries with MNFs@PEO as electrolytes both display great cycling stabilities with high-capacity retention, indicating their potential applications in lithium metal batteries. The study will put forward new inspirations for designing advanced MOF-based composite solid electrolytes.