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.

Two-Dimensional π-d Conjugated Conductive Metal-Organic Framework with Triple Active Centers as High-Performance Cathodes for Flexible Zinc Batteries.

Conductive metal-organic frameworks (C-MOFs) have received extensive interest in high-performance zinc-ion batteries (ZIBs) owing to multi-redox sites and high electrical conductivity. Here, we present a π-d C-MOF by coordinating 2,3,5,6-tetraaminobenzoquinone (TABQ) ligands with Cu2+ ions (2D Cu-TABQ) acting as cathodes for ZIBs. Benefiting from a triple active center (Cu2+, C=O, and C=N), 2D Cu-TABQ shows an ultra-high reversible capacity of 297.7 mAh g-1at 0.2 A g-1. Meanwhile, 2D Cu-TABQ also has superior cycle stability with a capacity of up to 98.2 mAh g-1 after 1000 times at 2.0 A g-1. Considering the instability of the ligand bonds of C-MOFs in aqueous electrolytes,this work uses gel electrolytes to reduce the dissolution of organic ligands into the electrolyte, thus suppressing the shuttle effect, significantly improving the cycling stability of 2D Cu-TABQ. The flexible battery assembled by 2D Cu-TABQ shows excellent capacity retention (64.4%) after 50 times at 0.2 A g-1, which is significantly better than 36.4% in the common electrolyte, as well as outstanding bending resistance and electrochemical properties at different folding angles. This investigation will highlight the electrochemical application of C-MOFs in flexible zinc ion batteries and offer novel ideas for the structural design of cathodes with multiple active centers.

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.

Bacterial Cellulose/Polyelectrolyte Complex Hydrogel Separator with Thermal and Dimensional Stabilities for Dendrite Suppression in Zinc Ion Battery

Bacterial Cellulose/Polyelectrolyte Complex Hydrogel Separator with Thermal and Dimensional Stabilities for Dendrite Suppression in Zinc Ion Battery

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.

Constructing Dual Schottky Junctions for High‐Performance Zinc Anode

AbstractAqueous zinc ion batteries provide new solutions for achieving environmentally friendly and safe energy storage devices. Unfortunately, the further application is hampered by the growth of zinc dendrites caused by uneven zinc deposition, hydrogen evolution and other side interfacial reactions at the zinc anode. Herein, a multifunctional Bi‐Bi2O3 hybrid artificial interface layer is constructed on the surface of the zinc anode using an in situ conversion reaction. Among them, the Bi‐Bi2O3 Schottky structure not only significantly accelerates the migration of Zn2+ through its built‐in electric field, but also effectively improves the hydrogen evolution barrier (ΔGH*), thereby suppressing side reactions. Moreover, the Schottky contact formed between the interface layer and the metal zinc interface also regulates the electronic distribution state on the zinc surface and optimizes the deposition process of Zn2+, ensuring a more uniform and orderly zinc deposition process. Based on the synergistic effect of dual Schottky junctions, symmetric batteries achieve stable cycling for 2000 h under the conditions of 1.0 mA cm−2 and 1.0 mAh cm−2. The full cell assembled with α‐MnO2 as the cathode maintains capacity of 112.7 mAh g−1 after 1000 cycles at 1 A g−1 with a capacity retention rate of 84%.

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.

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.

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.

Dual Redox Reactions of Silver Hexacyanoferrate Prussian Blue Analogue Enable Superior Electrochemical Performance for Zinc‐ion Storage**

AbstractPrussian blue analogues (PBAs) have been employed as host materials of aqueous zinc‐ion batteries (ZIBs), however, they suffer from low capacity and poor cycling stability due to limited electron transfer and the presence of interstitial water in PBAs. Herein, a vacancy and water‐free silver hexacyanoferrate K0.95Ag3.05Fe(CN)6 (AgHCF‐3) was synthesized by adjusting the ratio of K and Ag in the framework. It offers nearly four electrons involving two sequential redox reactions, namely, Fe3+/Fe2+ and Ag+/Ag0, to deliver a large capacity of 179.6 mAh g−1 at 20 mA g−1 with Coulomb efficiency of ~100 %. The Zn//AgHCF‐3 cell delivers an estimated energy density of 200 Wh kg−1, surpassing reported PBAs‐based ZIBs. The formation of Ag0 in the cycling process merits favorable rate performance of AgHCF‐3 (156.4 mAh g−1 at 200 mA g−1 with 80.3 % capacity retention after 100 cycles). This investigation paves new pathways for high‐capacity PBA cathodes.

Antifreezing functionalized-alginate-based electrolytes for zinc-ion batteries

Flexible zinc-ion batteries (ZIBs) assembled with hydrogel electrolyte are considered as promising flexible energy storage devices because of their inherent safety and versatility. However, the ionic conductivity and mechanical properties of most hydrogel electrolytes are not satisfactory, Furthermore, they will freeze at subzero temperature due to existing water. In this work, a freezing resistant polycarboxylic double network gel electrolyte (SIP-CS) with high ionic conductivity (14.36 mS cm⁻1 at −20 °C) and excellent mechanical property (fracture stress of 241.5 kPa and fracture strain of 1011 %) is prepared. Iminodiacetic acid (IDA) is applied to modify the alginate mainchains with many -COOH groups, which could provide channels for ion migration and endow hydrogel with high ionic conductivity. Additionally, sorbitol, containing lots of hydroxyl groups, is applied as a cryoprotectant to enhance the subzero performance of the electrolyte, because sorbitol could break the hydrogen bonds between water molecules, inhibit the formation of ice crystals, and reduce the freezing point of the gel electrolyte. The freezing point of SIP-CS is −37.0 °C, enabling the electrolyte to perform well at low temperatures. The flexible quasi solid Zn-MnO2 battery is assembled to evaluate the low-temperature electrochemical performance of SIP-CS. The assembled Zn-MnO2 battery shows good cycling and stable electrochemical performance, which proves the excellent antifreezing property of SIP-CS. This work provides a new strategy for preparing an electrolyte with good withstand low-temperature capability.

Sulfurized Composite Interphase Enables a Highly Reversible Zn Anode.

The stability and reversibility of Zn anode can be greatly improved by in-situ construction of solid electrolyte interphase (SEI) on Zn surface via a low-cost design strategy of ZnSO4 electrolyte. However, the role of hydrogen bond acceptor -SO3 accompanying ZnS formation during SEI reconstruction is overlooked. In this work, we have explored and revealed the new role of -SO3 and ZnS in the in-situ formed sulfide composite SEI (SCSEI) on Zn anode electrochemistry in ZnSO4 aqueous electrolytes. Structure characterization and DFT demonstrate that the introduction of -SO3 can not only reduce the dehydration energy of [Zn(H2O)6]2+, but also enhance the stability of the ZnS/Zn interface and homogenize the ZnS/Zn interface electric field, thereby significantly improving the dynamic kinetics and uniform deposition of Zn2+. Owing to the synergistic effect of ZnS and -SO3, a high cycling stability of 1500 h with a cumulative-plated capacity of 7.5 Ah cm-2 at 10 mA cm-2 has been achieved within the symmetrical cell. Furthermore, the full cell with NH4V4O10 cathode exhibits outstanding cyclic stability, exceeding 2000 cycles at 5 A g-1 and maintaining a Coulombic efficiency of 100%. These new insights into anionic synergistic strategy could significantly enhance the practical application of zinc-ion batteries.

Simultaneous Modulation on Solvation Shell and Electrode Interface for Reversible Zinc Anode Realized by a Mutiplefunctional Additive

AbstractThe inferior reversibility of Zn metal anode caused by undesired Zn dendrite and severe interfacial side reactions has to be addressed for the commercial application of Zinc ion batteries (ZIBs). Here, a multiple functional sodium benzaldehyde 2,4‐disulfonate(B24DADS) additives with various blocks of polar sulfonate group, Lewis basic aldehyde groups, and hydrophobic benzene ring is proposed to regulate the solvation structure of Zn2+, construct an H2O‐poor and zincophilic dual electric layer structure, and create a passive SEI on the Zn anode surface, thus restaining dendrite growth and interfacial side reactions. Furthermore, uniform deposition mechanics of the Zn are revealed by the synergistic effect of induced deposition, additive‐derived SEI formation, and texture regulation. In addition, Na+ can also limit the growth of zinc dendrites based on electrostatic shielding mechanisms. Therefore, the multifunctional B24DADS additive grants the anode to deliver remarkable electrochemical performance. Under critical test conditions (20 mA cm−2/20 mAh cm−2), the zinc provides superior long cycling (3700 h) with a low polarization voltage (0.02 V). B24DADS containing electrolyte is well matched with manganese dioxide cathode. This effort renders a promising way to explore advanced additives with unique molecular structures for addressing zinc dendrite growth and rampant side effects.

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.

Sn Penetrated Zincophilic Interface Design in Porous Zn Substrate for High Performance Zn-Ion Battery.

Rechargeable zinc-ion batteries are considered an ideal energy storage system due to their low cost and nonflammable aqueous electrolyte. However, dendrite growth, hydrogen evolution reaction, and self-corrosion of zinc anode brought about serious safety risks including short circuits and electrode expansion. Therefore, a modified host-design strategy with a 3D porous structure and bulk-phase penetrated zincophilic interface is proposed to boost the stability and lifetime of the Zn anode. The porous Zn substrate is constructed by universal HCl etching and the uniform and tight Sn-penetrated zincophilic interface is formed by effective electron beam evaporation (EBE). The porous substrate can uniform zinc ion flux and the Sn coating could effectively improve zinc ion deposition behavior, thus inhibiting the risk of dendrites growth and side reaction. As a result, the 3D Zn substrate with Sn interface (3D Zn@Sn) exhibits prolonged galvanostatic cycling performance up to 4500h with a low polarization of ≈25mV (1mAcm-2, 1mAhcm-2) in the symmetric cell. The full cell assembled with KVOH@Ti could maintain a high specific capacity of 148.6mAhg-1 after 500 galvanostatic cycles (10Ag-1). This work proposed an improved electrode design to realize the high performance of zinc ion batteries.

Porous V2CTx MXene as a High Stability Zinc Anode Protective Coating.

Aqueous Zn batteries exhibit significant research potential owing to their environmental friendliness and high energy density. Nevertheless, the formation of dendrites on the zinc anode and the sluggish diffusion kinetics of zinc ions adversely affect the cycle life of zinc ion batteries. In this study, we employ porous V2CTx (MVMX) as a protective layer for the zinc anode. The uniform porous structure of MVMX promotes active site exposure and facilitates the transport of zinc ions. Remarkably, the Zn@Ti half-cell demonstrated an average CE of 99.7% in 1500 cycles. Furthermore, the Zn-Zn symmetric battery exhibited stable cycling for 1600 h at current densities of 5 mA cm-2 and 1 mAh cm-2. Additionally, the MVMX@Zn||V2O5 full cell exhibited a capacity of 198 mAh g-1 and retained a capacity of 124.75 mAh g-1 after 5000 cycles at 1 A g-1, demonstrating the potential of employing alternative MXenes for fabricating stable zinc anodes.