Aqueous Zinc-ion Batteries Research Articles

Lattice Expanded Titania as an Excellent Anode for an Aqueous Zinc-Ion Battery Enabled by a Highly Reversible H+-Promoted Zn2+ Intercalation

Lattice Expanded Titania as an Excellent Anode for an Aqueous Zinc-Ion Battery Enabled by a Highly Reversible H⁺-Promoted Zn²⁺ Intercalation

Na Ions Doped Fe2VO4 Cathode for High Performance Aqueous Zinc-ion Batteries.

Aqueous zinc ion batteries are thought to be a new generation of secondary batteries that will replace lithium-ion batteries due to their great safety and inexpensive cost. In the cathode materials of aqueous zinc ion batteries with long life and high capacity, abundant active sites and crystal structure stability play an important role. In the present work, the strategy of Na+ intercalation of Fe2VO4 (FVO) is proposed, aiming at the insertion of Na+, which not only enriches the active sites, but also sodium and iron ions act as guest species with the negatively charged VOx lattice to provide strong electrostatic attraction to stabilize the lamellar structure. In terms of electrochemical performance, the discharge specific capacity is 370 mAh g-1 at a current density of 0.1 A g-1, and when the current density is arising 5 A g-1, the specific capacity also reaches 200 mAh g-1 after cycling 2000 with a capacity retention of 99 %, which is better than the electrochemical performance of Fe2VO4 (FVO) alone at 50 mAh g-1. The superior electrochemical performance proves that FVO-Na is an ideal cathode material for zinc ion batteries.

In-Situ Self-Respiratory Solid-to-Hydrogel Electrolyte Interface Evoked Well-Distributed Deposition on Zinc Anode for Highly Reversible Zinc-Ion Batteries.

The aqueous zinc-ion batteries (AZIB) have emerged as a promising technology in the realm of electrochemical energy storage. Despite its potential advantages in terms of safety, cost-effectiveness, and inherent safety, AZIB faces significant challenges. Issues attributed to unsupported thermodynamics and non-uniform potential distribution and deposition, present formidable obstacles that necessitate resolution. To tackle these challenges, a novel strategy adapting hybrid organic-inorganic in situ derived solid-to-hydrogel electrolyte interface (StHEI) has been developed from coordination reactions and self-respiratory process, establishing uniform diffusion channels by ion bridges and accelerating ion transport. Self-respiratory pattern of StHEI realized through in situ inorganic component conversion further prolongs the protecting duration, which effectively mitigates corrosion and passivation but enhance the mechanical properties of the StHEI measured through Young's modulus. This novel StHEI promotes well-distributed potential lines within the Helmholtz regions. Zn2+ are finally induced to deposit and nucleate in a compact, fine, and uniform manner. Asymmetrical batteries assembled with the modified Zn electrode and bare Zn exhibit exceptional stability over 3000 h (1 mA cm-2-0.5 mAh cm-2). The asymmetrical Cu//Zn cell achieved an outstanding average Coulombic efficiency (CE) of 99.6 % over 1200 cycles.

In‐Situ Self‐Respiratory Solid‐to‐Hydrogel Electrolyte Interface Evoked Well‐Distributed Deposition on Zinc Anode for Highly Reversible Zinc‐Ion Batteries

AbstractThe aqueous zinc‐ion batteries (AZIB) have emerged as a promising technology in the realm of electrochemical energy storage. Despite its potential advantages in terms of safety, cost‐effectiveness, and inherent safety, AZIB faces significant challenges. Issues attributed to unsupported thermodynamics and non‐uniform potential distribution and deposition, present formidable obstacles that necessitate resolution. To tackle these challenges, a novel strategy adapting hybrid organic–inorganic in situ derived solid‐to‐hydrogel electrolyte interface (StHEI) has been developed from coordination reactions and self‐respiratory process, establishing uniform diffusion channels by ion bridges and accelerating ion transport. Self‐respiratory pattern of StHEI realized through in situ inorganic component conversion further prolongs the protecting duration, which effectively mitigates corrosion and passivation but enhance the mechanical properties of the StHEI measured through Young's modulus. This novel StHEI promotes well‐distributed potential lines within the Helmholtz regions. Zn2+ are finally induced to deposit and nucleate in a compact, fine, and uniform manner. Asymmetrical batteries assembled with the modified Zn electrode and bare Zn exhibit exceptional stability over 3000 h (1 mA cm−2–0.5 mAh cm−2). The asymmetrical Cu//Zn cell achieved an outstanding average Coulombic efficiency (CE) of 99.6 % over 1200 cycles.

Eco-Friendly High-Performance Symmetric All-COF/Graphene Aqueous Zinc-Ion Batteries.

Developing high-performance aqueous symmetric all-organic batteries (SAOBs) by replacing metal-based batteries or batteries with organic electrolytes is highly attractive to achieve a greener rechargeable world. However, such a new energy storage system still exhibits unsatisfactory rate capability and cycling stability due to the limitations in electrode materials screening. Here, a novel covalent organic framework (COF) containing abundant CN and CO for the electrode material is designed, which is combined with graphene and assembled into all-COF/graphene batteries for the first time. Moreover, the co-storage of Zn2+ and H+ in COF can be achieved in a mild aqueous electrolyte. Impressively, benefiting from the extended porous structure of COF, plentiful active reaction sites, more extensive electron delocalization from CO modification at molecular level, as well as enhanced fast H+ storage capacity of graphene and CO in COF, this kind of SAOBs show excellent cycle life and high rate performance (over 15000 cycles with a capacity of 80 mAh g-1 at a high current density of 5 A g-1 in pouch cell). This work will open a new window for the design of high-performance aqueous organic batteries, further moving toward a more eco-friendly electrochemical world.

An Ultrahigh-Modulus Hydrogel Electrolyte for Dendrite-Free Zinc Ion Batteries.

Quasi-solid-state aqueous zinc ion batteries suffer from anodic zinc dendrite growth during plating/stripping processes, impeding their commercial application. The inhibition of zinc dendrites by high-modulus electrolytes has been proven to be effective. However, hydrogel electrolytes are difficult to achieve high modulus owing to their inherent high water contents. This work reports a hydrogel electrolyte with ultrahigh modulus that can overcome the growth stress of zinc dendrites through mechanical suppression effect. By combining wet-annealing, solvent-exchange, and salting-out processes and tuning the hydrophobic and crystalline domains, a hydrogel electrolyte is obtained with substantial water content (≈70%), high modulus (198.5MPa), high toughness (274.3MJ m-3), and high zinc-ion conductivity (28.9 mS cm-1), which significantly outperforms the previously reported poly(vinyl alcohol)-based hydrogels. As a result, the hydrogel electrolyte exhibits excellent dendrite-suppression effect and achieves stable performance in Zn||Zn symmetric batteries (1800h of cycle life at 1mA cm-2). Moreover, the Zn||V2O5 pouch batteries display excellent cycling life and operate stably even under extreme conditions, such as large bending angle (180°) and automotive crushing. This work provides a promising approach for designing mechanically reliable hydrogel electrolytes for advanced aqueous zinc ion batteries.

Synergistic Long-Term Protection of Inorganic and Polymer Hybrid Coatings for Free-Dendrite Zinc Anodes.

Constructing an artificial solid electrolyte interface protective layer on the surface of the zinc anode is an effective strategy for addressing dendrite growth, passivation, and the hydrogen evolution reaction in aqueous zinc-ion batteries. This study introduces a robust interlayer composed of a polyvinyl butyral matrix decorated with SiO2 particles (PS). Adsorption of water by Si-OH on the surface of SiO2 leads to excellent hydrophilicity and accelerates the desolvation of ions. A highly stable and hydrophilic PS coating enhances ion migration and possesses ultralong protection ability, ensuring uniform ion deposition and a lower nucleation barrier. Anodes protected by the PS coating achieve long-term cycling stability of >4000 h at 2 mA cm-2 in symmetric cells. The assembled PS-Zn//NH4V4O10 full cells exhibit superior electrochemical performance, demonstrating their potential for practical applications in rechargeable zinc batteries.

Polyethylene Glycol-Protected Zinc Microwall Arrays for Stable Zinc Anodes.

Aqueous zinc-ion batteries promise good commercial application prospects due to their environmental benignity and easy assembly under atmospheric conditions, positioning them as a viable alternative to lithium-ion batteries. However, some inherent issues, such as chaotic zinc dendrite growth and inevitable side reactions, challenge the commercialization progress. In this work, we imprint highly ordered zinc microwall arrays to regulate the electric field toward uniform Zn deposition. Afterward, coating a polyethylene glycol protection layer on the zinc microwalls aims to passivate the surface defects that rise unintentionally by mechanical imprinting. Polyethylene glycol can also boost oriented Zn deposition along the (002) plane and inhibit hydrogen gas production, further enhancing the stability of such three-dimensional (3D) hybrid anodes. Compared to the messy electric field near the polyethylene glycol-protected Zn foil, the uniform electric field provided by these 3D hybrid anodes can regulate the Zn deposition behaviors, enabling a longer lifespan and thus certifying the necessity of adding 3D microstructures. Additionally, 3D microstructures can offer a larger surface area than that of the planar Zn foil, providing more reaction sites and higher specific capacity. In this case, the 3D hybrid electrode exhibits a good initial capacity of approximately 120 mA h/g at a current density of 5 A/g and a nice retention of more than 80% after 800 cycles. The proposed scheme paves the way for a long-term stable 3D zinc anode solution with promising application prospects.

Basics and Advances of Manganese-Based Cathode Materials for Aqueous Zinc-Ion Batteries.

It is greatly crucial to develop low-cost energy storage candidates with high safety and stability to replace alkali metal systems for a sustainable future. Recently, aqueous zinc-ion batteries (ZIBs) have received tremendous interest owing to their low cost, high safety, wide oxidation states, and sophisticated fabrication process. Nanostructured manganese (Mn)-based oxides in different polymorphs are the potential cathode materials for the widespread application of ZIBs. However, Mn-based oxide materials suffer from several drawbacks, such as low electronic/ionic conductivity and poor cycling performance. To overcome these issues, various structural modification strategies have been adopted to enhance their electrochemical activity, including phase/defect engineering, doping with foreign atoms (e.g., metal and/or nonmetal atoms), and coupling with carbon materials or conducting polymers. Herein, this review targets to summarize the advantages and disadvantages of the above-mentioned strategies to improve the electrochemical performance of the cathodic part of ZIBs. The challenges and suggestions for the development of manganese oxides for ZIBs are put forward.

Ultrafast Tailoring Amorphous Zn0.25V2O5 with Precision‐Engineered Artificial Atomic‐Layer 1T′‐MoS2 Cathode Electrolyte Interphase for Advanced Aqueous Zinc‐Ion Batteries

AbstractVanadium (V)‐based oxides as cathode materials for aqueous zinc‐ion batteries (AZIBs) still encounter challenges such as sluggish Zn2+ diffusion kinetics and V‐dissolution, thus leading to severe capacity fading and limited life span. Here, we designed an ultrafast and facile colloidal chemical synthesis strategy based on crystalline Zn0.25V2O5 (c‐ZVO) to successfully prepare a‐ZVO@MoS2 core@shell heterostructures, where atomic‐layer MoS2 uniformly coats on the surface of amorphous a‐ZVO. The tailored amorphous structure of a‐ZVO provides more isotropic pathways and active sites for Zn2+, thus significantly enhancing the Zn2+ diffusion kinetics during charge–discharge processes. Meanwhile, as an efficient artificial cathode electrolyte interphase, the precision‐engineered atomic‐layer MoS2 with semi‐metallic 1T′ phase not only contributes to improved electron transport but also effectively inhibits the V‐dissolution of a‐ZVO. Therefore, the prepared a‐ZVO@MoS2 and conceptually validated a‐V2O5@MoS2 derived from commercial c‐V2O5 exhibit excellent cycling stability at an ultralow current density (0.05 A g−1) while maintaining good rate capability and capacity retention. This research achievement provides a new effective strategy for various amorphous cathode designs for AZIBs with superior performance.

A sustainable route: from wasted alkaline manganese batteries to high-performance cathode for aqueous zinc ion batteries

A sustainable route: from wasted alkaline manganese batteries to high-performance cathode for aqueous zinc ion batteries

"Anchoring Capture" Effect Mimicking Proline in Hardy Deep-Sea Fish to Stabilize the Zinc Anode with Lower Operating Temperature.

The low plating/stripping efficiency of zinc anodes, dendrite growth, and high freezing points of aqueous solutions hinder the practical application of aqueous zinc-ion batteries. This paper proposes a zwitterionic permeable network solid-state electrolyte based on the "anchor-capture" effect to address these problems by incorporating proline (Pro, a biological antifreeze agent) into the electrolyte. Extensive validation tests, Quantum Chemistry (QC) calculations, Molecular Dynamics (MD) Simulations, and ab initio molecular dynamics simulations consistently indicate that the amino groups in proline adsorb onto the Zn metal surface, stabilizing the zinc anode-electrolyte interface, suppressing side reactions from water decomposition, and homogenizing zinc-ion flux. This electrolyte demonstrates excellent reversibility in Zn-Mn2O3 cells and Zn-Zn half-cells, achieving a high coulombic efficiency of over 99.4% across 2000 cycles in Zn-Mn2O3 full cells, and delivering a discharge-specific capacity of 175.2 mAhg-1 at -35°C and 1 Ag-1. Additionally, an appropriate concentration of proline lowers the electrolyte's freezing point to -45°C through the network's solid-state effect, ensuring the stable operation of the solid-state battery at -35°C. This innovative concept of network solid-state electrolytes injects new vitality into the development of multifunctional solid-state electrolytes.

Biomineralization Inspired the Construction of Dense Spherical Stacks for Dendrite-Free Zinc Anodes.

Aqueous zinc-ion batteries (AZIBs) are considered to be one of the most promising energy storage systems due to their high degree of safety and low cost. However, the deposition of the uncontrolled zinc dendritic morphology on the surface of the Zn anode seriously reduces the cycle life of AZIBs. Herein, inspired by natural biomineralization, a uniform spherical zinc deposition is achieved via the addition of a biological macromolecule to the electrolyte. The proposed biological macromolecule makes Zn2+ undergo dense spherical deposition by regulating the relative growth rate of high-index planes of metal zinc, effectively avoiding the destruction from irregular zinc dendrites. The symmetric cell with the addition of such a biological macromolecule can be stably cycled for >3200 h at 1 mA cm-2 for 1 mAh cm-2. This work sheds light on expanding morphological regulation of metal deposition to spherical shapes for stable metal anodes in addition to a single-crystal plane control strategy.

Boosting de-solvation via halloysite nanotubes-cellulose composite separator for dendrite-free zinc anodes

Aqueous zinc-ion batteries (ZIBs) have attracted considerable attention owing to intrinsic advantages, which encompass inherent safety and a cost-effective manufacturing process. Nevertheless, the lifespan of Zn anodes is limited by inclement dendrite growth and adverse side reactions, impeding the commercial viability of ZIBs. In this study, we engineered a multifunctional cellulose-based separator (HC) synthesized from halloysite nanotubes (HNTs) and cellulose to address these challenges effectively. Leveraging the exceptional water adsorption capacity and the unique inner positive and outer negative tubular structure of HNTs molecules, the HC separator facilitates the de-solvation behavior of [Zn(H2O)6]2+ and promotes uniform deposition of Zn2+. Furthermore, the HC separator demonstrates superior wettability, excellent flexibility, and higher ionic conductivity, which further lead to dendrite-free zinc deposition, a 2700-h cycling lifespan, and a coulombic efficiency (CE) of 98.88 % after 100 cycles. Notably, the ZIBs incorporating the HC separator exhibit exceptional cycling performance, retaining 83.5 % of their capacity after 2000 cycles at 5 A g−1. This novel approach offers a valuable direction for the advancement of cost-effective and durable ZIBs.

Achieving Stable Orientational Zinc Deposition for Reversible Zinc Anode through Supramolecular Anchoring Mechanism.

Aqueous zinc-ion batteries have been impeded by the hydrogen evolution reaction (HER), uncontrolled zinc dendrites, and side reactions on the Zn anode. In this work, a Zn-polyphenol supramolecular network is rationally designed for stabilizing Zn anodes (ZPN@Zn) even at high current density. Theoretical calculations and experiments show that the zinc-polyphenol supramolecular layer effectively inhibits the hydrogen evolution reaction by capturing water molecules through strong hydrogen bonding networks while also facilitating the rapid replenishment of Zn2+ ions at the interface through supramolecular anchoring. Additionally, it results in preferential deposition of Zn on the (002) plane, thereby contributing to nondendritic and highly reversible Zn plating/stripping behaviors even under high rates. Concomitantly, the ZPN@Zn achieves superior stability of nearly 1200 h at a high current density of 20 mA cm-2 and maintains a high CE efficiency of 99.86% after 3000 cycles at 1 mAh cm-2 and 5 mA cm-2. Remarkably, the full cell assembled with ZPN@Zn and NaV3O8 (NVO) endures 25 000 cycles at 20 A g-1, achieving an impressive performance for the realization of dendrite-free Zn anodes by supramolecular modulation.

Molecular Chain Rearrangement of Natural Cellulose-based Artificial Interphase for Ultra-stable Zn Metal Anodes.

The unstable electrolyte-anode interface, plagued by parasitic side reactions and uncontrollable dendrite growth, severely hampers the practical implementation of aqueous zinc-ion batteries. To address these challenges, we developed a regenerated cellulose-based artificial interphase with synergistically optimized structure and surface chemistry on the Zn anode (RC@Zn), using a facile molecular chain rearrangement strategy. This RC interphase features a drastically increased amorphous region and more exposed active hydroxyl groups, facilitating rapid Zn2+ diffusionand homogeneous Zn2+ interface distribution, thereby enabling dendrite-free Zn deposition. Additionally, the compact texture and abundant negatively charged surface of the RC interphase effectively shield water molecules and harmful anions, completely preventing H2 evolution and Zn corrosion. The superior mechanical strength and adhesion of the RC interphase also accommodate the substantial volume changes of Zn anodes even under deep cycling conditions. Consequently,the RC@Zn electrode demonstrates an outstanding cycling lifespan of over 8000 hours at a high current density of 10 mA cm-2. Significantly, the electrode maintains stable cycling even at a 90% depth of discharge and ensures stable operation of full cells with a low negative/positive capacity ratio of 1.6. This study provides new solution to construct highly stable and deep cycling Zn metal anodes through interface engineering.

Ambient Synthesis of Vanadium-Based Prussian Blue Analogues Nanocubes for High-Performance and Durable Aqueous Zinc-Ion Batteries with Eutectic Electrolytes.

Prussian blue analogues (PBAs) have been widely studied in aqueous zinc-ion batteries (AZIBs) due to the characteristics of large specific surface area, open aperture, and straightforward synthesis. In this work, vanadium-based PBA nanocubes were firstly prepared using a mild in situ conversion strategy at room temperature without the protection of noble gas. Benefiting from the multiple-redox active sites of V3+/V4+, V4+/V5+, and Fe2+/Fe3+, the cathode exhibited an excellent discharge specific capacity of 200 mAh g-1 in AZIBs, which is much higher than those of other metal-based PBAs nanocubes. To further improve the long-term cycling stability of the V-PBA cathode, a high concentration water-in-salt electrolyte (4.5 M ZnSO4+3 M Zn(OTf)2), and a water-based eutectic electrolyte (5.55 M glucose+3 M Zn(OTf)2) were designed to successfully inhibit the dissolution of vanadium and improve the deposition of Zn2+ onto the zinc anode. More importantly, the assembled AZIBs maintained 55 % of their highest discharge specific capacity even after 10000 cycles at 10 A g-1 with superior rate capability. This study provides a new strategy for the preparation of pure PBA nanostructures and a new direction for enhancing the long-term cycling stability of PBA-based AZIBs at high current densities for industrialization prospects.

Inorganic‐Organic Composite Cathode Materials for Aqueous Zinc Ion Batteries

AbstractAs potential candidates for large‐scale energy storage systems, aqueous zinc‐ion batteries (AZIBs) have attracted more and more attention from researchers and investors. Tremendous efforts have been devoted to develop high‐efficient cathode materials for improving comprehensive performances of AZIBs. Recently reported inorganic‐organic composite (IOC) cathode materials exhibited excellent electrochemical performance and were generally superior to corresponding inorganic or organic cathode materials. This paper presents a timely review on recent progresses and challenges in IOCs for AZIBs. Preparation strategies of IOCs have been elaborated and categorized, recent advances and main working mechanisms of IOCs are exhibited with a focus on the analysis methods for mechanism studies, outlooks and challenges of IOC cathodes for AZIBs are outlined to guide their future development.

Molecular Synergistic Effects Mediate Efficient Interfacial Chemistry: Enabling Dendrite-Free Zinc Anode for Aqueous Zinc-Ion Batteries.

The primary cause of the accelerated battery failure in aqueous zinc-ion batteries (AZIBs) is the uncontrollable evolution of the zinc metal-electrolyte interface. In the present research on the development of multiadditives to ameliorate interfaces, it is challenging to elucidate the mechanisms of the various components. Additionally, the synergy among additive molecules is frequently disregarded, resulting in the combined efficacy of multiadditives that is unlikely to surpass the sum of each component. In this study, the "molecular synergistic effect" is employed, which is generated by two nonhomologous acid ester (NAE) additives in the double electrical layer microspace. Specifically, ethyl methyl carbonate (EMC) is more inclined to induce the oriented deposition of zinc metal by means of targeted adsorption with the zinc (002) crystal plane. Methyl acetate (MA) is more likely to enter the solvated shell of Zn2+ and will be profoundly reduced to produce SEI that is dominated by organic components under the "molecular synergistic effect" of EMC. Furthermore, MA persists in a spontaneous hydrolysis reaction, which serves to mitigate the pH increase caused by the hydrogen evolution reaction (HER) and further prevents the formation of byproducts. Consequently, the 1E1M electrolyte not only extends the cycle life of the zinc anode to 3140 cycles (1 mA h cm-2 and 1 mA cm-2) but also extends the life of the Zn//MnO2 full battery, with the capacity retention rate still at 89.9% after 700 cycles.

Mo‐Doped Perovskite Cathode Enables High‐Performance Cycling‐Stable Zinc‐Ion Batteries

AbstractManganese compounds have emerged as promising cathode materials for aqueous zinc‐ion batteries (AZIBs). But their broader applications are impeded by such cathodes' poor structure stability and sluggish ion transportation. Herein, these limitations are addressed by proposing high‐valence Mo doping regnant LaMnO3 perovskite oxide cathodes to develop high‐performance rate stable AZIBs. The optimized doped cathode contributes a highest specific capacity of 445 mAh g−1 at the current density of 0.5 A g−1, which maintains 206 mAh g−1 at 2 A g−1 and accompanies with a remarkable capacity retention of 114% beyond 1000 cycles for continuous charge/discharge process. The doping of multivalent Mo is revealed to boost the energy storage capacity and stabilize the electrode structure via various ex situ characterization and theoretical calculations. Importantly, the incorporation of Mo facilitates the acceleration of reaction kinetics and sufficient charge transfer with H+ and Zn2+ as dual charge carriers, where H+ plays a dominant role. This work provides a new perspective on developing innovative perovskite oxide cathodes with high‐valence metal doping for AZIBs.