Coupling dual metal active sites and low-solvation architecture toward high-performance aqueous ammonium-ion batteries.

Aqueous rechargeable ammonium-ion batteries (AIBs) possess the characteristics of safety, low cost, environmental friendliness, and fast diffusion kinetics. However, their energy density is often limited due to the low specific capacity of cathode materials and narrow electrochemical stability windows of electrolytes. Herein, high-performance aqueous AIBs were designed by coupling Fe-substituted manganese-based Prussian blue analog (FeMnHCF) cathodes and highly concentrated NH4CF3SO3 electrolytes. In FeMnHCF, Mn3+/Mn2+-N redox reaction at high potential was introduced, and two metal active redox species of Mn and Fe were achieved. To match such FeMnHCF cathodes, highly concentrated NH4CF3SO3 electrolyte was further developed, where NH4+ ion displays low-solvation structure because of the increased coordination number of CF3SO3- anions. Furthermore, the water molecules are confined by NH4+ and CF3SO3- ions in their solvation sheath, leading to weak interaction between water molecules and thus effectively extending the voltage window of electrolyte. Consequently, the FeMnHCF electrodes present high reversibility during the charge/discharge process. Moreover, owing to a small amount of free water in concentrated electrolyte, the dissolution of FeMnHCF is also inhibited. As a result, the assembled aqueous AIBs exhibit enhanced energy density, excellent rate capability, and stable cycling behavior. This work provides a creative route to construct high-performance aqueous AIBs.

Towards More Sustainable Aqueous Zinc-Ion Batteries.

Aqueous zinc-ion batteries (AZIBs) are considered as the promising candidates for large-scale energy storage because of their high safety, low cost and environmental benignity. The large-scale applications of AZIBs will inevitably result in a large amount of spent AZIBs, which not only induce the waste of resources, but also pose environmental risks. Therefore, sustainable AZIBs have to be considered to minimize the risk of environmental pollution and maximize the utilization of spent compounds. Herein, this minireview focuses on the sustainability of AZIBs from material design and recycling techniques. The structure and degradation mechanism of AZIBs are discussed to guide the recycling design of the materials. Subsequently, the sustainability of component materials in AZIBs is further analysed to pre-evaluate their recycling behaviors and mentor the selection of more sustainable component materials, including active materials in cathodes, Zn anodes, and aqueous electrolytes, respectively. According to the features of component materials, corresponding green and economic approaches are further proposed to realize the recycling of active materials in cathodes, Zn anodes and electrolytes, respectively. These advanced technologies endow the recycling of component materials with high efficiency and a closed-loop control, ensuring that AZIBs will be the promising candidates of sustainable energy storage devices. This review will offer insight into potential future directions in the design of sustainable AZIBs.

An Air-Rechargeable Zn/Organic Battery with Proton Storage.

Air-rechargeable zinc batteries are a promising candidate for self-powered battery systems since air is ubiquitous and cost-free. However, they are still in their infancy and their electrochemical performance is unsatisfactory due to the bottlenecks of materials and device design. Therefore, it is of great significance to develop creative air-rechargeable Zn battery systems. Herein, an air-rechargeable Zn battery with H+-based chemistry was developed in a mild ZnSO4 electrolyte for the first time, where benzo[i]benzo[6,7]quinoxalino[2,3-a]benzo[6,7]quinoxalino[2,3-c]phenazine-5,8,13,16,21,24-hexaone (BQPH) was employed as cathode material. In this Zn/BQPH battery, a Zn2+ coordination with adjacent C═O and C═N groups leads to an inhomogeneous charge distribution in the BQPH molecule, which induces the H+ uptake on the remaining four pairs of the C═O and C═N groups in subsequent discharge processes. Interestingly, the large potential difference between the discharged cathode of the Zn/BQPH battery and oxygen triggers the redox reaction between them spontaneously, in which the discharged cathode can be oxidized by oxygen in air. In this process, the cathode potential will gradually rise along with H+ removal, and the discharged Zn/BQPH battery can be air-recharged without an external power supply. As a result, the air-rechargeable Zn/BQPH batteries exhibit enhanced electrochemical performance by fast H+ uptake/removal. This work will broaden the horizons of air-rechargeable zinc batteries and provide a guidance to develop high-performance and sustainable aqueous self-powered systems.

Rational Design of ZnMn2 O4 Quantum Dots in a Carbon Framework for Durable Aqueous Zinc-Ion Batteries.

Manganese oxides are promising cathode materials for aqueous zinc-ion batteries (ZIBs) due to their high energy density and low cost. However, in their discharging processes, the Jahn-Teller effect and Mn3+ disproportionation often lead to irreversible structural transformation and Mn2+ dissolution, deteriorating the cycling stability of ZIBs. Herein, ZnMn2 O4 quantum dots (ZMO QDs) were introduced into a porous carbon framework by in-situ electrochemically inducing Mn-MIL-100-derived Mn3 O4 quantum dots and the carbon composite. In such ZMO QDs and carbon composite, the quantum dot structure endows ZnMn2 O4 with a shorter ion diffusion route and more active sites for Zn2+ . The conductive carbon framework is beneficial to the fast transport of electrons. Furthermore, at the interface between the ZMO QDs and the carbon matrix, the Mn-O-C bonds are formed. They can effectively suppress the Jahn-Teller effect and manganese dissolution of discharge products. Therefore, Zn/ZMO QD@C batteries display remarkably enhanced electrochemical performance.

Proton-Assisted Aqueous Manganese-Ion Battery Chemistry.

Aqueous manganese-ion batteries (MIBs) are promising energy storage systems because of the distinctive merits of Mn metal, in terms of high abundance, low cost, nontoxicity, high theoretical capacity and low redox potential. Conventional MIBs are based on the Mn2+ ion storage mechanism, whereas the capacity in cathode materials is generally limited due to the high charge density and large solvated ionic radius of Mn2+ ions in aqueous electrolytes. Herein, proton intercalation chemistry is introduced in aqueous MIBs, in which the layered Al0.1 V2 O5 ⋅1.5 H2 O (AlVO) cathode exhibits a consequent Mn2+ and H+ ion intercalation/extraction process. Such an energy storage mechanism contributes to enhanced electrochemical performance, including high capacity, fast reaction kinetics and stable cycling behavior. Benefiting from this proton intercalation chemistry, the aqueous Mn||AlVO cells could deliver high specific energy and power simultaneously. This work provides a route for the design of high-performance aqueous MIBs.

A Symmetric All-Organic Proton Battery in Mild Electrolyte.

All-organic proton batteries are attracting extensive attention due to their sustainability merits and excellent rate capability. Generally, strong acids (e.g. H2 SO4 ) have to be employed as the electrolytes to provide H+ for all-organic proton batteries due to the high H+ intercalation energy barrier. Until now, the design of all-organic proton batteries in mild electrolytes is still a challenge. Herein, a poly(2,9-dihydroquinoxalino[2,3-b]phenazine) (PO) molecule was designed and synthesized, where the adjacent C=N groups show two different chemical environments, resulting in two-step redox reactions. Moreover, the two reactions possess considerable voltage difference because of the large LUMO energy gap between PO and its reduction product. More impressively, the C=N groups endow the π-conjugated PO molecule with H+ uptake/removal in the ZnSO4 electrolyte. As a result, a symmetric all-organic proton battery is achieved in a mild electrolyte for the first time, which exhibits enhanced electrochemical performance and also broadens the chemistry of proton-based batteries.

Proton Chemistry Induced Long-Cycle Air Self-Charging Aqueous Batteries.

Air self-charging aqueous metal-ion batteries usually suffer from capacity loss after self-charging cycles due to the formation of basic salts on cathodes in the near-neutral electrolytes. Here, air self-charging Pb/pyrene-4,5,9,10-tetraone (PTO) batteries based on proton chemistry are developed in acidic electrolyte. The fast kinetics of H+ uptake/removal endows the battery with enhanced electrochemical performance. Owing to the high standard electrode potential of oxygen in acid electrolyte, the discharged cathodes are spontaneously oxidized by oxygen in air along with H+ extraction and thus achieve self-charging without external power supply. Notably, the air self-charging mechanism involved H+ -based redox can effectively avoid the generation of basic salts on self-charging electrodes and thus guarantee long-term self-charging/galvanostatic discharging cycles of Pb/PTO batteries. This work provides a promising strategy for designing long-cycle air self-charging systems.

An Ultralow Temperature Aqueous Battery with Proton Chemistry.

Conventional aqueous batteries usually suffer from serious capacity loss under subzero conditions owing to the freeze of electrolytes. To realize the utilization of aqueous batteries in extremely cold climates, low-temperature aqueous battery systems have to be developed. Herein, an aqueous Pb-quinone battery based on p-chloranil/reduced graphene oxide (PCHL-rGO) in H2 SO4 electrolyte is developed. Such aqueous Pb/PCHL-rGO batteries display H+ insertion chemistry, which endows the batteries with fast reaction kinetics and high rate capability. In addition, the hydrogen bonds between water molecules can be significantly damaged in electrolyte by modulating the interaction between SO4 2- and water molecules, lowering the freezing point of electrolyte. As a result, the Pb/PCHL-rGO batteries deliver extraordinary electrochemical performance even at -70 °C. This work will broaden the horizons of aqueous batteries and open up new opportunities to construct low-temperature aqueous batteries.

Design Strategies for High-Performance Aqueous Zn/Organic Batteries.

Organic electroactive compounds are attractive to serve as the cathode materials of aqueous zinc-ion batteries (ZIBs) because of their resource renewability, environmentally friendliness and structural diversity. Up to now, various organic electrode materials have been developed and different redox mechanisms are observed in aqueous Zn/organic battery systems. In this Minireview, we present the recent developments in the energy storage mechanisms and design of the organic electrode materials of aqueous ZIBs, including carbonyl compounds, imine compounds, conductive polymers, nitronyl nitroxides, organosulfur polymers and triphenylamine derivatives. Furthermore, we highlight the design strategies to improve their electrochemical performance in the aspects of specific capacity, output voltage, cycle life and rate capability. Finally, we discuss the challenges and future perspectives of aqueous Zn/organic batteries.

Electrochemically Induced Metal-Organic-Framework-Derived Amorphous V2 O5 for Superior Rate Aqueous Zinc-Ion Batteries.

The electrochemical performance of vanadium-oxide-based cathodes in aqueous zinc-ion batteries (ZIBs) depends on their degree of crystallinity and composite state with carbon materials. An in situ electrochemical induction strategy was developed to fabricate a metal-organic-framework-derived composite of amorphous V2 O5 and carbon materials (a-V2 O5 @C) for the first time, where V2 O5 is in an amorphous state and uniformly distributed in the carbon framework. The amorphous structure endows V2 O5 with more isotropic Zn2+ diffusion routes and active sites, resulting in fast Zn2+ transport and high specific capacity. The porous carbon framework provides a continuous electron transport pathway and ion diffusion channels. As a result, the a-V2 O5 @C composites display extraordinary electrochemical performance. This work will pave the way toward design of ZIB cathodes with superior rate performance.

Proton Insertion Chemistry of a Zinc-Organic Battery.

Proton storage in rechargeable aqueous zinc-ion batteries (ZIBs) is attracting extensive attention owing to the fast kinetics of H+ insertion/extraction. However, it has not been achieved in organic materials-based ZIBs with a mild electrolyte. Now, aqueous ZIBs based on diquinoxalino [2,3-a:2',3'-c] phenazine (HATN) in a mild electrolyte are developed. Electrochemical and structural analysis confirm for the first time that such Zn-HATN batteries experience a H+ uptake/removal behavior with highly reversible structural evolution of HATN. The H+ uptake/removal endows the Zn-HATN batteries with enhanced electrochemical performance. Proton insertion chemistry will broaden the horizons of aqueous Zn-organic batteries and open up new opportunities to construct high-performance ZIBs.

A rechargeable aqueous manganese-ion battery based on intercalation chemistry.

Aqueous rechargeable metal batteries are intrinsically safe due to the utilization of low-cost and non-flammable water-based electrolyte solutions. However, the discharge voltages of these electrochemical energy storage systems are often limited, thus, resulting in unsatisfactory energy density. Therefore, it is of paramount importance to investigate alternative aqueous metal battery systems to improve the discharge voltage. Herein, we report reversible manganese-ion intercalation chemistry in an aqueous electrolyte solution, where inorganic and organic compounds act as positive electrode active materials for Mn2+ storage when coupled with a Mn/carbon composite negative electrode. In one case, the layered Mn0.18V2O5·nH2O inorganic cathode demonstrates fast and reversible Mn2+ insertion/extraction due to the large lattice spacing, thus, enabling adequate power performances and stable cycling behavior. In the other case, the tetrachloro-1,4-benzoquinone organic cathode molecules undergo enolization during charge/discharge processes, thus, contributing to achieving a stable cell discharge plateau at about 1.37 V. Interestingly, the low redox potential of the Mn/Mn2+ redox couple vs. standard hydrogen electrode (i.e., -1.19 V) enables the production of aqueous manganese metal cells with operational voltages higher than their zinc metal counterparts.

A Universal Compensation Strategy to Anchor Polar Organic Molecules in Bilayered Hydrated Vanadates for Promoting Aqueous Zinc-Ion Storage.

The electrochemical performance of layered vanadium oxides is often improved by introducing guest species into their interlayer. Guest species with high stability in the interlayer and weak interaction with Zn2+ during charge/discharge process are desired to promoting reversible Zn2+ transfer. Herein, a universal compensation strategy was developed to introduce various polar organic molecules into the interlayer of Alx V2 O5 ·nH2 O by replacing partial crystal water. The high-polar groups in the organic molecules have a strong electrostatic attraction with pre-intercalated Al3+ , which ensures that organic molecules can be anchored in the interlayer of hydrated vanadates. Simultaneously, the low-polar groups endow organic molecules with a weak interaction with Zn2+ during cycling, thus liberalizing reversible Zn2+ transfer. As a result, Alx V2 O5 with polar organic molecules displays enhanced electrochemical performance. Furthermore, based on above cathode material, a pouch cell was assembled by further integrating a dendrite-free N-doped carbon nanofiber@Zn anode, displaying an energy density of 50 Wh kg-1 . This work provides a path for designing stable guest species with a weak interaction with Zn2+ in the interlayer of layered vanadium oxide towards high-performance cathode materials of aqueous Zn batteries.