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Aqueous zinc-ion batteries have become a promising energy storage battery due to high theoretical specific capacity, abundant zinc resources and low cost. However, zinc dendrite growth and hydrogen evolution reaction limit their application. This study aims to improve the cycling performance and stability of aqueous zinc-ion batteries by improving the gel electrolyte. Polyacrylamide (PAM) is selected as the base material of the gel electrolyte, which has good stability and safety, but the water retention capacity, Zn2+ migration number, and ionic conductivity of PAM are low, which affects the long-term stability of the battery. In response to these problems, we optimized PAM by chemical cross-linking method, and formed an enhanced PAM gel by adding disodium citrate dihydrate (SC). Experimental results show that the introduction of an appropriate amount of SC in the enhanced PAM gel electrolyte can significantly improve its electrochemical performance. The zinc-ion symmetric battery achieved a stable cycle of more than 2100 hours at a current density of 0.5 mA cm-2, which is mainly attributed to the inhibitory effect of the enhanced PAM gel on zinc dendrite growth and hydrogen evolution reaction. This study provides a new direction for the development and application of flexible zinc-ion batteries.
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High working voltage, large theoretical capacity and cheapness render Mn3O4 promising cathode candidate for aqueous zinc ion batteries (AZIBs). Unfortunately, poor electrochemical activity and bad structural stability lead to low capacity and unsatisfactory cycling performance. Herein, Mn3O4 material was fabricated through a facile precipitation reaction and divalent copper ions were introduced into the crystal framework, and ultra-small Cu-doped Mn3O4 nanocrystalline cathode materials with mixed valence states of Mn2+, Mn3+ and Mn4+ were obtained via post-calcination. The presence of Cu acts as structural stabilizer by partial substitution of Mn, as well as enhance the conductivity and reactivity of Mn3O4. Significantly, based on electrochemical investigations and ex-situ XPS characterization, a synergistic effect between copper and manganese was revealed in the Cu-doped Mn3O4, in which divalent Cu2+ can catalyze the transformation of Mn3+ and Mn4+ to divalent Mn2+, accompanied by the translation of Cu2+ to Cu0 and Cu+. Benefitting from the above advantages, the Mn3O4 cathode doped with moderate copper (abbreviated as CMO-2) delivers large discharge capacity of 352.9 mAh g-1 at 100 mA g-1, which is significantly better than Mn3O4 (only 247.8 mAh g-1). In addition, CMO-2 holds 203.3 mAh g-1 discharge capacity after 1000 cycles at 1 A g-1 with 98.6 % retention, and after 1000 cycles at 5 A g-1, it still performs decent discharge capacity of 104.2 mAh g-1. This work provides new ideas and approaches for constructing manganese-based AZIBs with long lifespan and high capacity.
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Aqueous zinc ion batteries (AZIBs) offer great potential for large-scale energy storage because of their high safety, low cost and acceptable energy density. However, the cycle life of AZIBs is inevitably affected by parasitic reactions and dendritic growth caused by multiple factors such as electrode, electrolyte and separator, which pose significant obstacles to the practical application of AZIBs. To address these challenges, conducting polymer (CP) based materials have gained widespread attention in the realm of rechargeable batteries due to the adjustable band gap, controllable morphology, and excellent flexibility of CPs. In particular, CPs exhibit remarkable conductivity, low dimensionality, and doping characteristics, making them highly promising for integration into the AZIB system. In this review, the problems associated with the cathode, anode, electrolyte, and separator of AZIBs are discussed, and the application of CPs for their modification is summarized. The review provides a comprehensive analysis of the action mechanisms involved in the CP modification process and offers valuable insights for the design and development of CPs that can be effectively utilized in AZIBs. Additionally, the review presents a promising outlook of this research field, aiming to further advance the application of low-cost and high-performance CPs and their composites in AZIBs.
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The Zn dendrite limits the practical application of aqueous zinc-ion batteries in the large-scale energy storage systems. To suppress the growth of Zn dendrites, a zinc ionophore of hydroxychloroquine (defined as HCQ) applied in vivo treatment is investigated as the electrolyte additive. HCQ dynamically regulates zinc ion concentration in the outer Helmholtz layer, promoting even Zn plating at the anode/electrolyte interface. This is evidenced by the scanning electron microscopy, which delivers planar Zn plating after cycling. It is further supported by the X-ray diffraction spectroscopy, which reveals the growth of Zn (002) plane. Additionally, the reduced production of H2 during Zn plating/stripping is detected by the in-situ differential electrochemical mass spectrometry (DEMS), which shows the resistance of Zn (002) to hydrogen evolution reaction. The mechanism of dynamic regulation for zinc ion concentration is demonstrated by the in-situ optical microscopy. The hydrated zinc ion can be further plated more rapidly to the uneven location than the case in other regions, which is resulted from the dynamic regulation for zinc ion concentration. Therefore, the uniform Zn plating is formed. A cycling life of 1100 h is exhibited in the Zn||Zn symmetric cell at 1.6 mA cm-2 with the capacity of 1.6 mAh cm-2. The Zn||Cu battery exhibits a cycling life of 200 cycles at 4 mA cm-2 with a capacity of 4 mAh cm-2 and the average Coulombic efficiency is larger than 99 %. The Zn||VO2 battery with HCQ modified electrolyte can operate for 1500 cycles at 4 A g-1 with a capacity retention of 90 %. This strategy in the present work is wished to advance the development of zinc-ion batteries for practical application.
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MnO2 is commonly used as the cathode material for aqueous zinc-ion batteries (AZIBs). The strong Coulombic interaction between Zn ions and the MnO2 lattice causes significant lattice distortion and, combined with the Jahn-Teller effect, results in Mn2+ dissolution and structural collapse. While proton intercalation can reduce lattice distortion, it changes the electrolyte pH, producing chemically inert byproducts. These issues greatly affect the reversibility of Zn2+ intercalation/extraction, leading to significant capacity degradation of MnO2. Herein, we propose a novel method to enhance the cycling stability of δ-MnO2 through selenium doping (Se-MnO2). Our work indicates that varying the selenium doping content can regulate the intercalation ratio of H+ in MnO2, thereby suppressing the formation of ZnMn2O4 by-products. Se doping mitigates the lattice strain of MnO2 during Zn2+ intercalation/deintercalation by reducing Mn-O octahedral distortion, modifying Mn-O bond length upon Zn2+ insertion, and alleviating Mn dissolution caused by the Jahn-Teller effect. The optimized Se-MnO2 (Se concentration of 0.8 at.%) deposited on carbon nanotube demonstrates a notable capacity of 386 mAh g-1 at 0.1 A g-1, with exceptional long-term cycle stability, retaining 102 mAh g-1 capacity after 5000 cycles at 3.0 A g-1.
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Manganous-manganic oxide (Mn3O4), akin to other manganese-based oxides, faces several critical challenges such as substantial capacity fading and limited rate performance due to its inferior electrical conductivity, in addition to the inevitable dissociation of Mn 2+ . To address these issues, we introduce for the first time a novel carbon-coated Mn3O4/Na2CO3 (Mn3O4/Na2CO3/C) composite material. Comprehensive characterizations indicate that Na2CO3 effectively curtails Mn 2+ dissolution, enhances carbon encapsulation throughout charging/discharging cycles, and exposes additional active sites on the Mn3O4/Na2CO3/C composite. Electrochemical assessments confirm that the Mn3O4/Na2CO3/C-2 cathode exhibits exceptional electrochemical performance, outperforming other cathodes in the ZnSO4 system. Moreover, the Mn3O4/Na2CO3/C-2 cathode delivers a high specific capacity of ~550 mAh g -1 at 0.1 A g -1 and maintains a significant capacity of ~230 mAh g -1 after 360 cycles at 1.0 A g -1 within the 2.0 M ZnSO4+0.2 M MnSO4 electrolyte system, demonstrating its potential as a high-performance cathode material for aqueous zinc-ion batteries.
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The aqueous zinc ion battery emerges as the promising candidate applied in large-scale energy storage system. However, Zn anode suffers from the issues including Zn dendrite, Hydrogen evolution reaction and corrosion. These challenges are primarily derived from the instability of anode/electrolyte interface, which is associated with the interfacial charge density distribution. In this context, the recent advancements concentrating on the strategies and mechanism to regulate charge density at the Zn anode/electrolyte interface are summarized. Different characterization techniques for charge density distribution have been analysed, which can be applied to assess the interfacial zinc ion transport. Additionally, the charge density regulations at the Zn anode/electrolyte interface are discussed, elucidating their roles in modulating electrostatic interactions, electric field, structure of solvated zinc ion and electric double layer, respectively. Finally, the perspectives and challenges on the further research are provided to establish the stable anode/electrolyte interface by focusing on charge density modifications, which is expected to facilitate the development of aqueous zinc ion battery.
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Interfacial chemical modification is an effective strategy to adjust the strong Coulombic ion-lattice interactions with high valence cations experienced by electrode materials, facilitating the reaction kinetic. In this paper, a simple and fast surface oxygen implantation strategy was designed to adjust the electronic structure of stainless steel (SS) supported vanadium diselenide (VSe2) nanosheets and form a surface protective film, which effectively accelerates the reaction kinetics of Zn2+ and extends the cycle life of the battery. It is demonstrated that the conductivity, pseudocapacitance and specific capacity can be tuned by selectively introducing oxygen species to the surface, which provides an important reference for the design of electrodes with controlled surface chemistry. Density functional theory (DFT) calculations also confirm that the electronic structure can be adjusted by surface oxygen injection strategy, which not only improves the conductivity, but also adjusts the adsorption energy, thus providing favorable conditions for zinc ion storage. Benefiting from the selenium vacancies and pores generated by the removal of part of selenium, and the oxide film formed on the surfaces, the VSe2-xOx-SS-30 electrode showed higher specific capacity (188.4 mAh/g at 0.5 A g-1 after 50 cycles), better rate performance (107.1 mAh/g at 4 A g-1) and more satisfactory cycling stability (83.1 mAh/g at 5 A g-1 after 1800 cycles) than VSe2-SS electrode. Importantly, the flexible quasi-solid-state VSe2-xOx-SS-30//Zn battery also exhibits high specific capacity and excellent environmental adaptability. Furthermore, the zinc (de)intercalation and transformation reactions mechanism was revealed by some ex-situ/in-situ techniques.
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Due to safety problems caused by the use of organic electrolytes in lithium-ion batteries and the high production cost brought by the limited lithium resources, water-based zinc-ion batteries have become a new research focus in the field of energy storage due to their low production cost, safety, efficiency, and environmental friendliness. This paper focused on vanadium dioxide and expanded graphite (EG) composite cathode materials. Given the cycling problem caused by the structural fragility of vanadium dioxide in zinc-ion batteries, the feasibility of preparing a new composite material is explored. The EG/VO2 composites were prepared by a simple hydrothermal method, and compared with the aqueous zinc-ion batteries assembled with a single type of VO2 under the same conditions, the electrode materials composited with high-purity sulfur-free expanded graphite showed more excellent capacity, cycling performance, and multiplicity performance, and the EG/VO2 composites possessed a high discharge ratio of 345 mAh g-1 at 0.1 A g-1, and the Coulombic efficiency was close to 100%. The EG/VO2 composite has a high specific discharge capacity of 345 mAh g-1 at 0.1 A g-1 with a Coulombic efficiency close to 100%, a capacity retention of 77% after 100 cycles, and 277.8 mAh g-1 with a capacity retention of 78% at a 20-fold increase in current density. The long cycle test data demonstrated that the composite with expanded graphite effectively improved the cycling performance of vanadium-based materials, and the composite maintained a stable Coulombic efficiency of 100% at a high current density of 2 A/g and still maintained a specific capacity of 108.9 mAh/g after 2000 cycles.
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The aqueous zinc ion battery (AZIB) has been widely studied due to its rapid kinetics and high specific capacity attributed to the chemical insertion of H+ protons. However, the current research landscape lacks comprehensive investigations into copper-based sulfide materials and the intricate co-embedding/extraction mechanism of H+/Zn2+. In this study, we employed an innovative in-situ etching method to synthesize a current collector-integrated Cu@Cu31S16 cathode material. Cu31S16 not only exhibits excellent stability and conductivity but also activates proton insertion chemistry. Consequently, we have demonstrated, for the first time, efficient and reversible co-embedding/extraction behavior of H+/Zn2+ in Zn-Cu31S16 batteries. Specifically, owing to the lower charging and discharging plateaus of zinc ions (0.65 V, 0.45 V) compared to H+ (0.97 V, 0.84 V) in Zn-Cu31S16 batteries, two distinct plateaus were observed. Moreover, we delved into the mechanism of ion co-embedding/extraction by exploring different ions (Zn2+, H+/Zn2+, H+) within varying voltage ranges. This exploration led to the development of three types of ion batteries, where Zn2+, H+/Zn2+, and H+ exhibit co-embedding/extraction within voltage ranges of 0.3-0.9 V, 0.3-1.05 V, and 0.5-1.05 V, respectively. These batteries have achieved impressive performance with specific capacities of 282.74 mAh g-1, 587.4 mAh g-1 and 687.3 mAh g-1, respectively. Introducing the concept of "Voltage-Selective Ion Co-Embedding/Extraction", this study broadens the research scope of AZIBs. This research not only offers a feasible solution and theoretical guidance for future proton batteries but also underscores the tremendous potential of AHPB.
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The design of aqueous zinc-ion batteries (ZIBs) that have high specific capacity and long-term stability is essential for future large-scale energy storage systems. Cathode materials with extended π-conjugation and abundant active sites are desirable to enhance the charge storage performance and the cycling stability of the aqueous ZIB. Based on this concept, 6,9-dihydropyrazino[2,3-g]quinoxaline-2,3,7,8(1H,4H)-tetrone was chosen as the monomer to be electropolymerized onto carbon cloth (PDHPQ-Tetrone/CC). When used as the cathode material for aqueous ZIBs, an exceptional cycling life (>20,000 cycles) at a current density of 10 A g-1 was achieved, with the specific capacity maintained at 82.8% and with the Coulombic efficiency at around 100% throughout cycling. At the charge-discharge current density of 0.1 A g-1, the ZIB with PDHPQ-Tetrone/CC achieved a high specific capacity of 248 mAh g-1. Kinetic analyses showed that both surface-capacitive-controlled processes and semi-infinite diffusion-controlled processes contribute to the stored charge. The charge storage mechanism was investigated with ex situ characterizations and involves the redox processes of carbonyl/hydroxyl and amino/imino groups coupled with insertion and extraction of both Zn2+ and H+.
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Aqueous zinc ion batteries (AZIBs) with metallic Zn anode have the potential for large-scale energy storage application due to their cost-effectiveness, safety, environmental-friendliness, and ease of preparation. However, the concerns regarding dendrite growth and side reactions on Zn anode surface hamper the commercialization of AZIBs. This review aims to give a comprehensive evaluation of the protective interphase construction and provide guidance to further improve the electrochemical performance of AZIBs. The failure behaviors of the Zn metal anode including dendrite growth, corrosion, and hydrogen evolution are analyzed. Then, the applications and mechanisms of the constructed interphases are introduced, which are classified by the material species. The fabrication methods of the artificial interfaces are summarized and evaluated, including the in-situ strategy and ex-situ strategy. Finally, the characterization means are discussed to give a full view for the study of Zn anode protection. Based on the analysis of this review, a stable and high-performance Zn anode could be designed by carefully choosing applied material, corresponding protective mechanism, and appropriate construction technique. Additionally, this review for Zn anode modification and construction techniques for anode protection in AZIBs may be helpful in other aqueous metal batteries with similar problems.
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Polyaniline (PANI) has been widely used as a cathode in aqueous zinc-ion batteries (AZIBs) because of its attractive conductivity and energy storage capability. However, the extensive application of PANI is limited by spontaneous deprotonation and slow diffusion kinetics. Herein, an 18-crown-6-functionalised PANI pseudorotaxane (18C6@PANI) cathode is successfully developed through a facile template-directed polymerisation reaction. The 18C6@PANI cathode exhibits a high specific capacity of 256 mAh g-1 at 0.2 A/g, excellent rate performance of 134 mAh g-1 at 6 A/g and outstanding cycle stability at a high current density of 3 A/g over 10,000 cycles. Experimental and theoretical analyses demonstrate the formation of the -N-Zn-O- structure. The abundant supramolecular channels in pseudorotaxane, induced by crown ether functional groups, are beneficial for achieving superior cyclability and rate capability. These encouraging results highlight the potential for designing more efficient PANI-based cathodes for high-performance AZIBs.
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Metal zinc (Zn) is being explored as a possible anode for aqueous zinc ion batteries (AZIBs). However, unrestrained Zn dendrite caused by "tip effect" and chemical corrosion continue to plague the Zn deposition process, limiting the functionality of AZIBs and prohibiting their use at high current densities. This work presents an in situ approach for introducing homogeneous ZnO nanoarrays onto the surface of Zn foil (Zn@ZnO NAs) as a functional protective interphase. On the one hand, well-distributed ZnO NAs protection layer can regulate the "tip effect" and confine the growth of Zn dendrite. On the other hand, the ZnO NAs layer can enhance the desolvation and diffusion process of Zn2+ on the surface of anode, attributing to low voltage hysteresis and exceptional electrochemical performance at high current densities. As a result, the Zn@ZnO NAs exhibits a low voltage hysteresis of 50.8 mV with a superb lifespan of 1200 h at a current density of 5 mA cm-2. Moreover, Zn@ZnO NAs||α-MnO2 full-cell shows a superior cycling performance after 500 cycles at 0.5 A g-1 with a capacity of 216.69 mAh g-1. This work is expected to provide ideas for designing other reversible zinc anode chemical systems, especially under a high current density.
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Resolving the sluggish transport kinetics of divalent Zn2+ in the cathode lattice and improving mass-loading performance are crucial for advancing the zinc-ion batteries (AZIBs) application. Herein, PEO-LiV3O8 superlattice nanosheets (PEO-LVO) with expanded interlayer spacing (1.16 nm) are fabricated to provide a high-rate, stable lifetime, and large mass-loading cathode. The steady in-plane expansion without shrinkage after the first cycle, but reversible H+/Zn2+ co-insertion in PEO-LVO are demonstrated by operando synchrotron X-ray diffraction and ex situ characterizations. Moreover, the large capacity of PEO-LVO is traced back to the optimized Zn2+ insertion chemistry with increased Zn2+ storage ratio, which is facilitated by the interlayer PEO in lowering the Zn2+ diffusion barrier and increased number of active sites from additional interfaces, as anticipated by density functional theory. Due to the optimized ion insertion resulting in stalled interfacial byproducts and rapid kinetics, PEO-LVO achieves excellent high mass-loading performance (areal capacity up to 6.18 mAh cm-2 for freestanding electrode with 24 mg cm-2 mass-loading and 2.8 mAh cm-2 at 130 mA cm-2 for conventional electrode with 27 mg cm-2 mass-loading). As a proof-of-concept, the flexible all-solid-state fiber-shaped AZIBs with high mass-loading woven into a fabric can power an electronic watch, highlighting the application potential of PEO-LVO cathode.
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Vanadium nitride (VN) is a potential cathode material with high capacity and high energy density for aqueous zinc batteries (AZIBs). However, the slow kinetics resulting from the strong electrostatic interaction of the electrode materials with zinc ions is a major challenge for fast storage. Here, VN clusters with nitrogen-vacancy embedded in carbon (C) (Nv-VN/C-SS-2) are prepared for the first time to improve the slow reaction kinetics. The nitrogen vacancies can effectively accelerate the reaction kinetics, reduce the electrochemical polarization, and improve the performance. The density functional theory (DFT) calculations also prove that the rapid adsorption and desorption of zinc ions on Nv-VN/C-SS-2 can release more electrons to the delocalized electron cloud of the material, thus adding more active sites. The Nv-VN/C-SS-2 exhibits a specific capacity and outstanding cycle life. Meanwhile, the quasi-solid-state battery exhibits a high capacity of 186.5 mAh g-1, ultra-high energy density of 278.9 Wh kg-1, and a high power density of 2375.1 W kg-1 at 2.5 A g-1, showing excellent electrochemical performance. This work provides a meaningful reference value for improving the comprehensive electrochemical performance of VN through interface engineering.
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Aqueous zinc-ion batteries (ZIBs) are the new generation electrochemical energy storage systems. Recently, two-dimensional conductive metal-organic frameworks (2D c-MOFs) are attractive to serve as cathode materials of ZIBs due to their compositional diversity, abundant active sites, and excellent conductivity. Despite the growing interest in 2D c-MOFs, their application prospects are still to be explored. Herein, a tetraoxa[8]circulene (TOC) derivative with unique electronic structure and interesting redox-active property are synthesized to construct c-MOFs. A series of novel 2D c-MOFs (Cu-TOC, Zn-TOC and Mn-TOC) with different conductivities and packing modes are obtained by combining the linker tetraoxa[8]circulenes-2,3,5,6,8,9,11,12-octaol (8OH-TOC) and corresponding metal ions. Three c-MOFs all exhibit typical semiconducting properties, and Cu-TOC exhibits the highest electrical conductivity of 0.2 S cm-1 among them. Furthermore, their electrochemical performance as cathode materials for ZIBs have been investigated. They all performed high reversible capacity, decent cycle stability and excellent rate capability. This work reveals the key insights into the electrochemical application potential of 2D c-MOFs and advances their development as cathode materials in ZIBs.
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Rechargeable aqueous zinc-ion batteries (AZIBs) have been highly desired due to their low cost, intrinsic safety, environmental friendliness, and great potential in large-scale power storage systems. However, their practical applications are impeded by unstable long-term electrochemical performances induced by microstructure degradation of the cathode material, hydrogen evolution reaction in the electrolyte, and dendritic growth on the zinc anode upon cycling. In this work, rubidium cations (Rb+) are introduced to synthesize an Rb+-preintercalated NH4V4O10 (NVO-Rb) composite. The contribution of Rb+ ions as pillars in V-O interlayers to facilitating Zn2+ storage is investigated first, and then the influences of partial Rb+ ions from the NVO-Rb cathode on the aqueous electrolyte and zinc anode are specially inspected from different viewpoints. Based on a series of characterization results, it is comprehensively elucidated that the partial Rb+ ions into the electrolyte suppress the generation of byproducts on the cathode and regulate the dendrite growth on the zinc anode, thus effectively promoting the long-term electrochemical performances of NVO-based AZIBs. The assembled Znâ¥Zn(CF3SO3)2â¥NVO-Rb cell can exhibit a high specific capacity and optimized Zn2+ diffusion kinetics, especially an improved electrochemical cyclability with a capacity retention of 87.6% at 5 A g-1 over 10000 cycles. This study enlightens the multiple roles of cation-preintercalation in the layered structure material and provides a feasible strategy for the development of high-performance aqueous batteries.
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Aqueous zinc ion batteries have been extensively researched due to their distinctive advantages such as low cost and high safety. Vanadium oxides are important cathode materials, however, poor cycle life caused by vanadium dissolution limits their application. Recent studies show that the lattice NH4 + in vanadium oxides can act as a pillar to enhance structural stability and play a crucial role in improving its cycling stability. Nevertheless, there is still a lack of research on the effect of the lattice NH4 + content on structural evolution and electrochemical performance. Herein, we synthesize vanadium oxides with different contents of lattice NH4 + by a one-step hydrothermal reaction. The vanadium oxides with lattice NH4 + exhibit high initial capacity, as well as good cycling stability and rate performance compared to bare vanadium oxide. Combined with electrochemical analyses, ex-situ structural characterizations, and in-situ X-ray diffraction tests, we reveal that the lattice NH4 + content plays a positive role in vanadium oxides' structural stability and cation diffusion kinetics. This work presents a direction for designing high-performance vanadium cathodes for aqueous zinc ion batteries.
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Two-dimensional (2D) transition metal borides (MBenes), new members of the 2D materials family, hold great promise for use in the electrocatalytic and energy storage fields because of their high specific area, high chemical activity, and fast charge carrier mobility. Although various types of MBenes are reported, layered MBenes featuring redox-active terminal groups for high energy output are not yet produced. A facile and energy-efficient method for synthesizing MBenes equipped with redox-active terminal groups for cascade Zn||I2 batteries is presented. Layered MBenes have ordered metal vacancies and âBr terminal groups, enabling the sequential reactions of I-/I0 and Br-/Br0. The I2-hosting MBene-Br cathode results in a specific energy as high as 485.8 Wh kg-1 at 899.7 W kg-1 and a specific power as high as 6007.7 W kg-1 at 180.2 Wh kg-1, far exceeding the best records for Zn||I2 batteries. The results of this study demonstrate that the challenges of MBene synthesis can be overcome and reveal an efficient path for producing high-performance redox-active electrode materials for energy-dense cascade aqueous batteries.