Metal Ions versus Protons: Tracking of Charge-Carrier Insertion into a Cathode Oxide in Aqueous Rechargeable Batteries

Protons in aqueous electrolytes can perform as an additional type of charge carrier for insertion/extraction in addition to the primary carrier cations in aqueous rechargeable batteries. Despite many diverse claims regarding the effect of protons, mutually conflicting experimental results and their interpretations without direct evidence have been reported over the last decade. Systematic examinations and analyses are thus imperative to clarify the conditions of proton insertion in aqueous rechargeable batteries. Utilizing V₂O₅ as a model cathode and beaker-type cells with a sufficient amount of ZnSO₄ aqueous electrolytes in this work, it is demonstrated that protons are inserted into the cathode prior to Zn-ions in low-pH conditions (pH ≤ 3.0). In stark contrast, the influence of protons on the discharge voltage and capacity is insignificant, when either the pH becomes higher (pH ≥ 4.0) or the electrolyte volume is considerably low in coin-type cells. Similar behavior of pH-dependent proton insertion is also verified in Na–, Mg–, and Al-ion electrolytes. Providing a resolution to the controversy regarding proton insertion, the present study emphasizes that the influence of protons substantially varies depending on the pH and relative volume of electrolytes in aqueous batteries.     

Cathode Design for Aqueous Rechargeable Multivalent Ion Batteries: Challenges and Opportunities

With the rapid growth in energy consumption, renewable energy is a promising solution. However, renewable energy (e.g., wind, solar, and tidal) is discontinuous and irregular by nature, which poses new challenges to the new generation of large-scale energy storage devices. Rechargeable batteries using aqueous electrolyte and multivalent ion charge are considered more suitable candidates compared to lithium-ion and lead-acid batteries, owing to their low cost, ease of manufacture, good safety, and environmentally benign characteristics. However, some substantial challenges hinder the development of aqueous rechargeable multivalent ion batteries (AMVIBs), including the narrow stable electrochemical window of water (≈1.23 V), sluggish ion diffusion kinetics, and stability issues of electrode materials. To address these challenges, a range of encouraging strategies has been developed in recent years, in the aspects of electrolyte optimization, material structure engineering and theoretical investigations. To inspire new research directions, this review focuses on the latest advances in cathode materials for aqueous batteries based on the multivalent ions (Zn²⁺, Mg²⁺, Ca²⁺, Al³⁺), their common challenges, and promising strategies for improvement. In addition, further suggestions for development directions and a comparison of the different AMVIBs are covered.     

Hydrated Layered Vanadium Oxide as a Highly Reversible Cathode for Rechargeable Aqueous Zinc Batteries

Rechargeable aqueous zinc batteries have gained considerable attention for large‐scale energy storage systems because of their low cost and high safety, but they suffer from limitations in cycling stability and energy density with advanced cathode materials. Here, a high‐performance V₅O₁₂·6H₂O (VOH) nanobelt cathode uniformly located on a stainless‐steel substrate via a facile electrodeposition technique is reported. We show that the hydrated layered VOH cathode enables highly reversible and ultrafast Zn²⁺ cation (de)intercalation processes, as confirmed by various electrochemical, X‐ray diffraction, X‐ray photoelectron spectroscopy, and transmission electron microscopy analyses. It is demonstrated that the binder‐free VOH cathode can deliver a discharge capacity of 354.8 mAh g^?1 at 0.5 A g^?1 with a high initial Coulombic efficiency of 99.5%, a high energy density of 194 Wh kg^?1 at 2100 W kg^?1, and a long cycle life with a capacity retention of 94% over 1000 cycles. In addition, a flexible quasi‐solid‐state Zn–VOH battery is constructed, achieving a reversible capacity of ≈300 mAh g^?1 with a capacity retention of 96% after 50 cycles and displaying excellent electrochemical behaviors under different bending states. This work sheds light on the development of rechargeable aqueous zinc batteries for stationary grid storage applications or flexible energy storage devices.     

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

Aqueous 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.     

Stable Aqueous Anode-Free Zinc Batteries Enabled by Interfacial Engineering

Anode-free zinc batteries (AFZBs) are proposed as promising energy storage systems due to their high energy density, inherent safety, low cost, and simplified fabrication process. However, rapid capacity fading caused by the side reactions between the in situ formed zinc metal anode and electrolyte hinders their practical applications. To address these issues, aqueous AFZBs enabled by electrolyte engineering to form a stable interphase are designed. By introducing a multifunctional zinc fluoride (ZnF₂) additive into the electrolyte, a stable F-rich interfacial layer is formed. This interfacial layer can not only regulate the growth orientation of zinc crystals, but also serve as an inert protection layer against side reactions such as H₂ generation. Based on these synergy effects, zinc deposition/dissolution with high reversibility (Coulombic efficiency > 99.87%) and stable cycling performance up to 600 h of are achieved in the electrolyte optimized by ZnF₂. With this electrolyte, the cycling life of AFZBs is significantly improved. The work may initiate the research of AFZBs and be useful for the design of high energy, high safety, and low-cost power sources.     

Ultrafast Rechargeable Aqueous Zinc-Ion Batteries Based on Stable Radical Chemistry

Aqueous zinc-ion batteries (ZIBs) are a promising candidate for fast-charging energy-storage systems due to its attractive ionic conductivity of water-based electrolyte, high theoretical energy density, and low cost. Current strategies toward high-rate ZIBs mainly focus on the improvement of ionic or electron conductivity within cathodes. However, enhancing intrinsic electrochemical reaction kinetics of active materials to achieve fast Zn²⁺ storage has been greatly omitted. Herein, for the first time, stable radical intermediate generation is demonstrated in a typical organic electrode material (methylene blue [MB]), which effectively decreases the reaction energy barrier and enhances the intrinsic kinetics of MB cathode, enabling ultrafast Zn²⁺ storage. Meanwhile, anionic co-intercalation essentially avoids MB molecules rearranging their configuration and sharing Zn²⁺ with adjacent functional groups, thus keeps the structure stable. As a result, Zn–MB batteries exhibit an excellent rate capability up to 500C and ultralong life of 20 000 cycles with a negligible 0.07% capacity decay per cycle at 100C, which is superior to that of most reported aqueous ZIBs batteries. This work provides a novel strategy of stable radical chemistry for ultrafast-charging aqueous ZIBs, which can be introduced to other appropriate organic materials and multivalent ion battery systems.     

Gel Polymer Electrolyte toward Large-Scale Application of Aqueous Zinc Batteries

Aqueous zinc batteries are promising candidates for energy storage and conversion devices in the “post-lithium” era due to their high energy density, high safety, and low cost. The electrolyte plays an important role in zinc batteries by conducting and separating the positive and negative electrodes. However, the issues of zinc dendrites growth, corrosion, by-product formation, hydrogen evolution and leakage, and evaporation of the aqueous electrolytes affect the commercialization of the batteries. Moreover, the widely used aqueous electrolytes result in large battery sizes, which are not conducive to the emerging smart devices. The intrinsic properties of gel polymer electrolytes (GPEs) can solve the above problems. In order to promote the wider application of GPEs-based zinc batteries, in this review, the working principle and the current problems of zinc batteries are first introduced, andthe merits of GPEs compared to aqueous electrolytes are then summarized. Subsequently, a series of challenges and corresponding strategies faced by GPE is discussed, and an outlook for its future development is finally proposed.     

Low-Cost Multi-Function Electrolyte Additive Enabling Highly Stable Interfacial Chemical Environment for Highly Reversible Aqueous Zinc Ion Batteries

The practicality of aqueous zinc ion batteries (AZIBs) for large-scale energy storage is hindered by challenges associated with zinc anodes. In this study, a low-cost and multi-function electrolyte additive, cetyltrimethyl ammonium bromide (CTAB), is presented to address these issues. CTAB adsorbs onto the zinc anode surface, regulating Zn²⁺ deposition orientation and inhibiting dendrite formation. It also modifies the solvation structure of Zn²⁺ to reduce water reactivity and minimize side reactions. Additionally, CTAB optimizes key physicochemical parameters of the electrolyte, enhancing the stability of the electrode/electrolyte interface and promoting reversibility in AZIBs. Theoretical simulations combined with operando synchrotron radiation-based in situ Fourier transform infrared spectra and in situ electrochemical impedance spectra further confirm the modified Zn²⁺ coordination environment and the adsorption effect of CTAB cations at the anode/electrolyte interface. As a result, the assembled Zn-MnO₂ battery demonstrates a remarkable specific capacity of 126.56 mAh g⁻¹ at a high current density of 4 A g⁻¹ after 1000 cycles. This work highlights the potential of CTAB as a promising solution for improving the performance and practicality of AZIBs for large-scale energy storage applications.     

Stabilizing the Interphase in Cobalt-Free,Ultrahigh-Nickel Cathodes for Lithium-Ion Batteries

High-nickel layered oxide cathodes, such as LiNi_1-x-yMn_xCo_yO₂ (NMC) and LiNi_1-x-yCo_xAl_yO₂ (NCA), are at the forefront for implementation in high-energy-density lithium-ion batteries. The presence of cobalt in both cathode chemistries, however, largely deters their application due to fiscal and humanitarian issues affiliated with cobalt sourcing. Increasing the Ni content drives down the Co content, but introduces additional structural and electrochemical problems attributed to high-Ni cathodes. Herein a dually modified cobalt-free ultrahigh-nickel cathode 0.02B-LiNi_0.99Mg_0.01O₂ (NBM) is presented with 1 mol% Mg and 2 mol% B that exhibits a high initial 1C discharge capacity of 210 mA h g⁻¹ with a 20% capacity retention improvement over 500 cycles when benchmarked against LiNiO₂ (LNO) in pouch full cell configurations with graphite anode. Postmortem analyses reveal the enhanced performance stems from reduced active lithium inventory loss and localized surface reactivity in the NBM cathode. The stabilized cathode-electrolyte interphase subsequently reduces transition-metal dissolution and ensuing chemical crossover to the graphite anode, which prevents further catalyzed parasitic reactions that harmfully passivate the anode surface. Altogether, this study aims to highlight the importance of electrode characterization and analysis from an interphasial viewpoint and to push the ongoing research to stabilize cobalt-free ultrahigh-Ni cathodes for industrial feasibility.     

Sn Alloying to Inhibit Hydrogen Evolution of Zn Metal Anode in Rechargeable Aqueous Batteries

The detrimental hydrogen evolution side reaction is one of the major issues hindering the commercialization of Zn metal anode in high-safety and low-cost rechargeable aqueous batteries. Herein, the authors present a Sn alloying approach to effectively inhibit the hydrogen evolution and dendrite growth of the Zn metal anode. Through in situ monitoring of the hydrogen production during repeated plating/stripping tests, it is quantitatively demonstrated that the hydrogen evolution of alloy electrode with appropriate Sn amount is only half of that of pure Zn electrode. Furthermore, the Sn alloying allows for favorable Zn nucleation sites, lowering the Zn nucleation energy barrier and promoting more uniform Zn deposition. The Zn-Sn alloy electrode offers much-improved plating/stripping cycling, that is, over 240 h at 5 mA cm^?2 and 35.2% depth of discharge. This work provides a practically viable strategy to stabilize Zn metal electrode in rechargeable aqueous batteries.     

Reconstruction of Electric Double Layer for Long-Life Aqueous Zinc Metal Batteries

Aqueous rechargeable Zn metal batteries (AZMBs) have attracted widespread attention due to their intrinsic high volumetric capacity and low cost. However, the unstable Zn/electrolyte interface causes Zn dendrite growth and side reactions, resulting in poor Coulombic efficiency and unsatisfactory lifespan. Herein, a SiO₂ reinforced-sodium alginate (SA) hybrid film is designed to regulate solid–liquid interaction energy and spatial distribution of all species in the electric double layer (EDL) near the Zn electrode. The unique interfacial layer gives rise to a uniform distribution of Zn²⁺ in the Helmholtz layer through solvation sheath modulation. Moreover, theoretical calculations show that the SO₄²⁻ anions and free-water are substantially reduced in the Helmholtz layer, effectively suppressing hydrogen evolution reaction and formation of by-products through strong charge repulsion and hydrogen bond fixing of free-water. The reconfigured EDL not only ensures homogenous and fast Zn²⁺ transport kinetics for dendrite-free Zn deposition, but also eliminates interface parasitic side reactions. The Zn@SiO₂-SA electrode enables excellent cycling stability of symmetrical cells and high-loading full AZMBs with a lifespan over 3000 h and an areal capacity of 2.05 mAh cm⁻², thus laying a solid basis for realizing practical AZMBs.     

Tuning Electrochemical Properties of Nitroaromatic Cathodes by Function-Oriented Design for Rechargeable Lithium-Ion Batteries

Rechargeable lithium-ion batteries (LIBs) based on organic cathodes are an attractive alternative energy storage technology owing to the low cost and sustainability. Recently, nitro functionality in dinitrobenzenes is successfully demonstrated as an electrochemically reversible high-capacity redox group. In this study, a function-oriented design is employed to further disclose the effects of substituting functional groups and molecular conjugate structures on electrochemical properties of a range of nitroaromatic derivatives as organic cathodes for rechargeable LIBs. In specific, it is revealed that the redox potential of nitroaromatic cathodes can be effectively adjusted by introducing distinct electronically inducible functional groups, while the cyclic life can be significantly prolonged with the introduction of the hydrophilic groups. When constructed with extended π-conjugated structures, the electronic conductivity and electrochemical kinetics of nitroaromatics are increased significantly owing to their various long-range π–π stacking. Moreover, density-functional theory calculations further provide theoretical insights into the distinct electrochemical behaviors of the various nitroaromatics in the molecular level. This is the first study that reveals the influences of substituting groups and conjugated structures on the electrochemical performance of nitroaromatic cathode materials, which enables a function-oriented molecular design of such organic materials and sheds light on their future development.     

Application of 2D MXene in Organic Electrode Materials for Rechargeable Batteries: Recent Progress and Perspectives

Organic electrode materials (OEMs) are emerging green power because of the promising advantages such as environmental friendliness, abundant sources, easy recycling, and structural diversity. However, several inherent issues, including low electronic conductivity, dissolution of active materials, and particle pulverization restrict their practical application. MXene, as a novel 2D material has exhibited enormous potential to solve the issues of OEMs due to its high conductivity, unique structure, exceptional mechanical property, and abundant surface groups. Up to now, various effective strategies have been presented and achieved positive effects, such as constructing heterojunction structures, in situ assembly, dip-coating, preparing free-standing MXene paper, etc. Nonetheless, comprehensive review of the progress and status is rare. Herein, an overview of the application of MXene in organic electrode materials for rechargeable batteries is systematically put forward. Meanwhile, recent progress and future development directions are presented. This review can serve as a guide for future research.     

High-Energy-Density Quinone-Based Electrodes with [Al(OTF)]2+ Storage Mechanism for Rechargeable Aqueous Aluminum Batteries

Rechargeable aqueous aluminum batteries (AABs) are potential candidates for future large-scale energy storage due to their large capacity and the high abundance of aluminum. However, AABs face the challenges of inferior rate capability and cycling life due to the high charge density of Al³⁺, which induces the sluggish intercalation/extraction dynamics and structure collapse of inorganic cathode materials during discharge–charge cycles. Here, the optimization of macrocyclic calix[4]quinone (C4Q) with a large cavity and multi-adjacent carbonyls structure from quinone compounds to become excellent cathode materials for high-energy-density AABs is reported. It exhibits a high capacity of 400 mAh g⁻¹, a high rate capability (300 mAh g⁻¹ at 800 mA g⁻¹), and an excellent low-temperature performance (224 mAh g⁻¹ at − 20  ° C). The combination of experiments and theoretical calculations proves that Al(OTF)²⁺ cations coordinate with the carbonyl groups of C4Q during the discharge process, which can reduce desolvation penalty. Moreover, the fabricated pouch-type Al-C4Q battery delivers an energy density of 93 Wh kg⁻¹_cell, showing great potential for large-scale applications. This work is expected to facilitate the application of organic cathode for AABs.     

Achieving Synergetic Anion-Cation Redox Chemistry in Freestanding Amorphous Vanadium Oxysulfide Cathodes toward Ultrafast and Stable Aqueous Zinc-Ion Batteries

Flexible aqueous zinc-ion batteries (AZIBs) with high safety and low cost hold great promise for potential applications in wearable electronics, but the strong electrostatic interaction between Zn²⁺ and crystalline structures, and the traditional cathodes with single cationic redox center remain stumbling blocks to developing high-performance AZIBs. Herein, freestanding amorphous vanadium oxysulfide (AVSO) cathodes with abundant defects and auxiliary anionic redox centers are developed via in situ anodic oxidation strategy. The well-designed amorphous AVSO cathodes demonstrate numerous Zn²⁺ isotropic pathways and rapid reaction kinetics, performing a high reversible capacity of 538.7 mAhg^-1 and high-rate capability (237.8 mAhg^-1@40Ag^-1). Experimental results and theoretical simulations reveal that vanadium cations serve as the main redox centers while sulfur anions in AVSO cathode as the supporting redox centers to compensate local electron-transfer ability of active sites. Significantly, the amorphous structure with sulfur chemistry can tolerate volumetric change upon Zn²⁺/H⁺ insertion and weaken electrostatic interaction between Zn²⁺ and host materials. Consequently, the AVSO composites display alleviated structural degradation and exceptional long-term cyclability (89.8% retention after 20 000 cycles at 40 Ag^-1). This work can be generally extended to various freestanding amorphous cathode materials of multiple redox reactions, inspiring development of designing ultrafast and long-life wearable AZIBs.     

Controlling Vanadate Nanofiber Interlayer via Intercalation with Conducting Polymers: Cathode Material Design for Rechargeable Aqueous Zinc Ion Batteries

Aqueous zinc ion batteries (ZIBs) are promising energy storage devices due to the high ionic conductivity of the aqueous electrolyte as well as the safety, eco-friendliness, and low cost. Vanadium oxide-based materials are attractive cathode materials for aqueous ZIBs because of their high capacity from their layered structure and multiple valences. However, it is difficult to achieve high cycle stability and rate capability due to the low electrical conductivity and trapping of diffused electrolyte cations within the crystal structure, limiting the commercialization of aqueous ZIBs. In this study, the authors propose a facile sonochemical method for controlling the interlayer of the vanadate nanofiber crystal structure using poly(3,4-ethylene dioxythiophene) (PEDOT) to overcome the shortcomings of vanadium oxide-based materials. In addition, the electrochemical correlation between the interplanar distance of the expanded vanadate layers by the insertion of PEDOT and the behavior of Zn²⁺ ions is investigated. As a result, the intercalation of the conducting polymer increases the electron pathway and extends the distance of the vanadate layers, which helps to increase the number of active sites inside the vanadate and accelerate the zinc ion intercalation/de-intercalation process. Their findings may guide research on the next generation of ZIBs that can replace lithium ion batteries.     

Hierarchical Carbon–Nitrogen Architectures with Both Mesopores and Macrochannels as Excellent Cathodes for Rechargeable Li–O2 Batteries

Lithium–oxygen batteries are attracting more and more interest; however, their poor rechargeability and low efficiency remain critical barriers to practical applications. Herein, hierarchical carbon–nitrogen architectures with both macrochannels and mesopores are prepared through an economical and environmentally benign sol–gel route, which show high electrocatalytic activity and stable cyclability over 160 cycles as cathodes for Li–O₂ batteries. Such good performance owes to the coexistence of macrochannels and mesopores in C–N hierarchical architectures, which greatly facilitate the Li⁺ diffusion and electrolyte immersion, as well as provide an effective space for O₂ diffusion and O₂/Li₂O₂ conversion. Additionally, the mechanism of oxygen reduction reactions is discussed with the N‐rich carbon materials through first‐principles computations. The lithiated pyridinic N provides excellent O₂ adsorption and activation sites, and thus catalyzes the electrode processes. Therefore, hierarchical carbon–nitrogen architectures with both macrochannels and mesopores are promising cathodes for Li–O₂ batteries.     

A Targeted Functional Design for Highly Efficient and Stable Cathodes for Rechargeable Li‐Ion Batteries

Despite the great success of Li‐ion batteries (LIBs) up to now, higher demand has been raised with the emergence of the new generation electrics, such as portable devices and electrical vehicles. Even with the improvement on anodes, the cathodes with high capacity and long‐lastingness still remain a challenge. New 3D NiCo₂O₄@V₂O₅ core–shell arrays (CSAs) on carbon cloth as cathodes in LIBs have been reported in this work. The nanodesigned materials realize the theoretical specific capacity of V₂O₅ with high power rate based on the total mass of the framework and amount of active materials. The electrodes achieve superb cycling stability, among the most stable cathodes for LIBs ever reported. From both in situ transmission electron microscopy and quantum level calculations, the 3D NiCo₂O₄ nanosheet frameworks provide high electron conductivity and the skeleton of the robust CSAs without participating in the lithiation/delithiation; the thickness of the layered V₂O₅ plays a key role for Li diffusivity and the capacity contribution of electrodes. The structures herein point to new design concepts for high‐performance nanoarchitectures for LIB cathodes.     

Nanostructured Li2MnSiO4/C Cathodes with Hierarchical Macro‐/Mesoporosity for Lithium‐Ion Batteries

Li₂MnSiO₄/C nanocomposite with hierarchical macroporosity is prepared with poly(methyl methacrylate) (PMMA) colloidal crystals as a sacrificial hard‐template and water‐soluble phenol‐formaldehyde (PF) resin as the carbon source. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analyses confirm that the periodic macropores are ≈400 nm in diameter with 20–40 nm walls comprising Li₂MnSiO₄/C nanocrystals that produce additional large mesopores (< 30 nm) between the nanocrystals. The nanostructured Li₂MnSiO₄/C cathode exhibits a high reversible discharge capacity of 200 mAh g^?1 at C/10 (16 mA g^?1) rate at 1.5–4.8 V at 45 °C. Although the discharge capacity can be further increased on operating at 55 °C, the sample exhibits a relatively fast capacity fade at 55 °C, which can be partially solved by simply narrowing the voltage window to avoid side reactions of the electrolyte. The good performance of the Li₂MnSiO₄/C cathodes is attributed to the unique macro‐/mesostructure of the silicate coupled with uniform carbon coating.     

Antifreezing Hydrogel with High Zinc Reversibility for Flexible and Durable Aqueous Batteries by Cooperative Hydrated Cations

Hydrogels are widely used in flexible aqueous batteries due to their liquid‐like ion transportation abilities and solid‐like mechanical properties. Their potential applications in flexible and wearable electronics introduce a fundamental challenge: how to lower the freezing point of hydrogels to preserve these merits without sacrificing hydrogels' basic advantages in low cost and high safety. Moreover, zinc as an ideal anode in aqueous batteries suffers from low reversibility because of the formation of insulative byproducts, which is mainly caused by hydrogen evolution via extensive hydration of zinc ions. This, in principle, requires the suppression of hydration, which induces an undesirable increase in the freezing point of hydrogels. Here, it is demonstrated that cooperatively hydrated cations, zinc and lithium ions in hydrogels, are very effective in addressing the above challenges. This simple but unique hydrogel not only enables a 98% capacity retention upon cooling down to ?20 °C from room temperature but also allows a near 100% capacity retention with >99.5% Coulombic efficiency over 500 cycles at ?20 °C. In addition, the strengthened mechanical properties of the hydrogel under subzero temperatures result in excellent durability under various harsh deformations after the freezing process.