Rechargeable Aqueous Zinc-ion Batteries Research Articles

Bio‐Inspired Isoalloxazine Redox Moieties for Rechargeable Aqueous Zinc‐Ion Batteries

Organic electrode materials hold great potential for fabricating sustainable energy storage systems, however, the development of organic redox-active moieties for rechargeable aqueous zinc-ion batteries is still at an early stage. Here, we report a bio-inspired riboflavin-based aqueous zinc-ion battery utilizing an isoalloxazine ring as the redox center for the first time. This battery exhibits a high capacity of 145.5 mAh g-1 at 0.01 A g-1 and a long-life stability of 3000 cycles at 5 A g-1 . We demonstrate that isoalloxazine moieties are active centers for reversible zinc-ion storage by using optical and photoelectron spectroscopies as well as theoretical calculations. Through molecule-structure tailoring of riboflavin, the obtained alloxazine and lumazine molecules exhibit much higher theoretical capacities of 250.3 and 326.6 mAh g-1 , respectively. Our work offers an effective redox-active moiety for aqueous zinc batteries and will enrich the valuable material pool for electrode design.

Bi-Cation Electrolyte for a 1.7 V Aqueous Zn Ion Battery.

Rechargeable aqueous zinc-ion batteries (ZIBs) are receiving increased attention because of their high safety and low cost. However, their practical application is plagued by their low energy density as a result of low output voltage and a narrow voltage window of aqueous electrolytes. Here, we explored a ZIB with a wider potential window using bication (1 M Al(CF3SO3)3/1 M Zn(CF3SO3)2) as the electrolyte and α-MnO2 as the cathode, obtaining a discharge voltage of 1.7 V, ∼0.3 V higher than the value reported earlier. The resultant cell delivers a record high energy density of 448 W h kg-1 (based on MnO2 mass) and retains 100% capacity over 1000 cycles. The ion-storage mechanism and the role of Al3+ in enlarging the output voltage were elucidated. This research indicates the important role of using bications in improving the electrochemical performance of aqueous ZIBs, opening a new way to increase the energy density of aqueous energy storage devices.

High-performance Na1.25V3O8 nanosheets for aqueous zinc-ion battery by electrochemical induced de-sodium at high voltage

Aqueous rechargeable zinc-ion batteries (ARZIBs) are expected to replace organic electrolyte batteries owing to its low price, safe and environmentally friendly characteristics. Herein, we fabricated vanadium-based Na1.25V3O8 nanosheets as a cathode material for ARZIBs, which present a high performance by electrochemical de-sodium at high voltage to form Na2V6O16 phase in the first cycle: high capacity of 390mAh/g at 0.1 A/g, high rate performance (162mAh/g at 10 A/g) and superior cycle stability (179mAh/g with a high capacity retention of 88.2% of the maximum capacity after 2000 cycles). In addition, the cell exhibits a high energy density of 416.9 Wh/kg at 143.6W/kg, suggesting great potential of the as-prepared Na1.25V3O8 nanosheets for ARZIBs

Facile hydrothermal synthesis and electrochemical properties of (NH4)2V6O16 nanobelts for aqueous rechargeable zinc ion batteries

Aqueous rechargeable Zn-ion batteries (ARZIBs) have attracted great attention owing to many advantages including environmental protection, low cost and safety. Ammonium vanadates with multi-oxidation valence and open-framework layered structure, which is beneficial for zinc storage performance, are chosen as alternative candidates of cathode materials. (NH4)2V6O16 has received some attention in Li-ion battery, however, the electrochemical properties of (NH4)2V6O16 applied to ARZIBs has rarely reported comparatively. In this work, (NH4)2V6O16 nanobelts are prepared through a facile hydrothermal method and reported as the cathode material in ARZIBs. The Zn/(NH4)2V6O16 battery displays a wonderful rate capability with a staged reversible capacity of 322.0, 300.8, 267.5, 239.3, 209.2 mA h g−1 at 0.1, 0.2, 0.5, 1, 2 A g−1, respectively. The battery exhibits a high energy density (249 W h kg−1) and a long-term reversible cycling performance (78.3 % retained at 5 A g−1 after 2000 cycles). The complete morphology of (NH4)2V6O16 after long-term cycle also illustrates its good flexibility during Zn2+ insertion/extraction without structural damage. Multiple analytical measurements methods are applied to investigate the major reaction mechanisms of the Zn2+ reversible (de)intercalation. The results demonstrate that the (NH4)2V6O16 as a cathode substitute is very promising for ARZIBs or other advanced battery systems.

Rechargeable Aqueous Zinc-Ion Batteries in MgSO4/ZnSO4 Hybrid Electrolytes

HighlightsDivalent magnesium ions as electrolyte additives are first used to improve the performance of vanadium-based cathodes for aqueous ZIBs.Pre-adding magnesium ions into electrolytes provide an appropriate equilibrium balance between the dissolution and recombination of magnesium vanadates, thus suppress the continuous dissolution of active materials, and lead to a higher stability of the electrode.The hybrid aqueous electrolytes with cost-effective ZnSO4 and MgSO4 salts show a better competitive prospective for the stationary grid-scale applications.

Urchin-like Spinel MgV2O4 as a Cathode Material for Aqueous Zinc-Ion Batteries

The rechargeable aqueous zinc-ion battery is a promising candidate for energy storage demands owing to its low cost, intrinsic safety, and ecofriendliness. However, existing aqueous zinc-ion batter...

Boosting aqueous zinc-ion storage in MoS2 via controllable phase

Recently, aqueous rechargeable Zn-ion batteries have attracted extensive attention, owing to their low-cost, high operational safety and environmental friendliness. However, the aqueous zinc-ion battery is still in a very infant stage, and the main challenge is to develop the ideal cathode due to the sluggish kinetics and low reversibility of divalent zinc ions. Herein, for the first time, we report controllable phase engineered few-layered MoS2 nanosheet as cathode materials for rechargeable aqueous Zn-ion batteries and systematically study their performance. We found that the obtained MoS2 with different phase contents showed distinct performance in the rechargeable aqueous zinc-ion battery. In particular, the MoS2 nanosheets with ~70% 1T phase content displays excellent specific capacity and shows outstanding long-term cyclic stability. The mechanisms involved were clarified by not only comprehensive characterizations, but also the density functional theory (DFT) simulations that reveal the 1T phase MoS2 has much lower Zn diffusion energy barriers. This study provides new insight into the effect of different phases on the performance of MoS2-based electrodes and will improve our understanding of developing better cathodes for the aqueous rechargeable Zn-ion batteries.

Novel Charging-Optimized Cathode for a Fast and High-Capacity Zinc-Ion Battery

Rechargeable aqueous zinc-ion battery (ZIB) is one of attractive candidates for large-scale energy storage. Its further application relies on the exploitation of high-capacity cathode and the understanding of intrinsic energy storage mechanism. Herein, we report a novel layered K2V3O8 cathode material for ZIB, adopting a strategy of charging firstly to extract part of K-ions from vanadate in initial few cycles, which creates more electrochemical active sites and lowers charge transfer resistance of ZIB system. As results, a considerable specific capacity of 302.8 mAh g-1 at 0.1 A g-1 is achieved, as well as remarkable cycling stability (92.3% capacity retention at 4 A g-1 for 2000 cycles) and good rate capability. Besides, the energy storage mechanism was studied by in-situ X-ray diffraction, in-situ Raman spectra, X-ray photoelectron spectroscopy and inductively coupled plasma. An irreversible K-ions deintercalation in the first charge process is proved. It is believed that this novel ZIB's cathode material and the optimizing strategy will shine lights on developing next-generation large-scale energy storage devices.

Excellent Rate Capability and Cycling Stability of Novel H2V3O8 Doped with Graphene Materials Used in New Aqueous Zinc-Ion Batteries

Nanorods of H2V3O8 wrapped in graphene sheets were prepared by hydrothermal synthesis and tested as the cathode in an aqueous rechargeable zinc-ion battery. Cyclic voltammetry indicates that H2V3O8...

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.

MnO2 particles grown on the surface of N-doped hollow porous carbon nanospheres for aqueous rechargeable zinc ion batteries

The growing demand for energy storage devices leads to great interest in advanced batteries researches. Among them, aqueous rechargeable zinc ion batteries (ARZIBs) has attracted wide attention due to their low cost, simple manufacturing process and environmental friendliness. Here, we prepared a composite material, namely MnO2 particles grown on the surface of N-doped hollow porous carbon nanospheres, that is, combining hollow carbon material with metal oxides, and employed it as the cathode of ARZIBs. Owing to the synergistic merits of desirable structural features of manganese oxides and hollow porous carbon nanospheres, the composite material exhibited excellent performance for the storage of zinc ions, including high capacity of 206 mA h g−1 at 100 mA g−1, impressive rate capability of 103 mA h g−1 at 500 mA g−1 and superior cycling stability with the coulombic efficiency (capacity retention) of 98.3% over 650 cycles. The distinguished electrochemical behavior is attributed to the synergistic effects of desirable structural features of manganese oxides and hollow porous carbon nanospheres, which can be summed up as larger electron modified interface, high mass loading, and stable carbon-layer structure. These results demonstrate that the composite material could satisfy the criteria for applying in advanced ARZIBs.

VO2(B) nanobelts and reduced graphene oxides composites as cathode materials for low-cost rechargeable aqueous zinc ion batteries

Low-cost and high-safety aqueous zinc ion batteries show their potential application for a large-scale energy storage system due to the high capacity and stable Zinc metal anode. Herein, VO2(B)/reduce graphene oxide (RGO) composite is designed and synthesized via a facile simple hydrothermal reaction. VO2(B) nanobelts uniformly deposited on RGO nanoflakes, which provide an electronic transport pathway and prevent the collapse of the structure during the zinc ion (de)intercalation process. VO2(B)/RGO composite exhibits a remarkable capacity of 456 mAh g−1 at 100 mA g−1, an impressive rate capability of 292 mAh g−1 at 5 A g−1 and capable cycling stability. The existence of capacitive contribution leads to fast zinc ions storage behavior. Moreover, the VO2(B)/RGO composite also offers a maximum energy density of 317 Wh kg−1 at a power density of 70 W kg−1 (based on the mass of the positive electrode). It suggests that VO2(B)/RGO composite is a suitable cathode for zinc ion batteries.

Porous hydrated ammonium vanadate as a novel cathode for aqueous rechargeable Zn-ion batteries.

Development of suitable cathodes for use in aqueous rechargeable zinc ion batteries has attracted extensive interest. Herein, the electrochemical and structural changes of a novel porous hydrated ammonium vanadate (AVO) cathode in an aqueous ZnSO4-based electrolyte are reported. The AVO/Zn system exhibits a high reversible capacity of 418 mA h g-1, excellent long-term cyclability, and outstanding storage performance. Moreover, an interesting insertion mechanism with ternary carriers in a Zn/AVO aqueous rechargeable zinc-ion battery has been demonstrated for the first time.

Dendrite-free Zn anodes enabled by functional nitrogen-doped carbon protective layers for aqueous zinc-ion batteries.

Rechargeable aqueous zinc-ion batteries possess the merits of good environmental benignity, high operational safety and high energy density. Nevertheless, the practical application of zinc-ion batteries is severely obstructed by the inhomogeneous deposition of metallic Zn on the anode, which results in serious capacity fading, poor coulombic efficiency, and electrolyte consumption. Herein, we propose a simple strategy of constructing a functional nitrogen-doped carbon network coating layer on zinc foil for dendrite-free Zn stripping/plating. On one hand, the good conductivity of the artificial Zn/electrolyte interface can quickly balance the electric field and lower the nucleation overpotential. On the other hand, the porosity feature and functional groups of the protective layer can provide a fast Zn2+ transportation pathway and generate well-dispersed nucleation seeds. Therefore, the protective layer can effectively hamper the growth of metallic Zn dendrites and resist side reactions. The as-prepared N-C/Zn anode displays superior cycling stability (800 h at 2 mA cm-2 with the capacity of 2 mA h cm-2) and a satisfactory coulombic efficiency of 98.76% during the Zn stripping/plating process. A long cycle life and high specific capacity (162.10 mA h g-1 after 500 cycles at 2.0 A g-1) are also obtained for N-C/Zn||ZnSO4||V2O5 full cells. The strategy provides a facile and effective opportunity for constructing high-performance rechargeable aqueous zinc-ion batteries.

Electrochemical transformation reaction of Cu–MnO in aqueous rechargeable zinc-ion batteries for high performance and long cycle life

Rechargeable aqueous zinc-ion batteries (ZIBs) are emerging as an alternative to lithium-ion batteries in large-scale energy storage applications due to their safety and environmental friendliness.

Mn2O3/Al2O3 cathode material derived from a metal-organic framework with enhanced cycling performance for aqueous zinc-ion batteries.

Rechargeable aqueous zinc-ion batteries (ZIBs) are considered to be potential candidates for large-scale energy storage due to their high capacity, low cost, high safety and environmental friendliness. A key problem encountered in Mn-based cathodes is the dissolution of Mn2+ that causes significant capacity fading. Herein, a novel Mn2O3/Al2O3 composite material with a microbundle structure was synthesized using a strategy called 'MOFs as precursors'. Uniform distribution of Mn2O3 and Al2O3 with a precise controlled Mn/Al molar ratio can be easily realized using this method. After compositing with Al2O3, the resulting material shows not only a higher capacity but also a better cycling stability (118.0 mA h g-1 after 1100 cycles at 1500 mA g-1) than the pure Mn2O3. Combined with the ICP analysis, it can be deduced that Al2O3 can effectively inhibit the dissolution of Mn2+ from Mn3+ disproportionation. Our result can provide some inspiration for the modification of Mn-based materials and other materials used in zinc ion batteries or other battery systems.

Highly stable Zn metal anodes enabled by atomic layer deposited Al2O3 coating for aqueous zinc-ion batteries

Nanoscale Al2O3 coating by an atomic layer deposition technique enabled safe and dendrite-free Zn anodes for rechargeable aqueous zinc-ion batteries.

A Deep-Cycle Aqueous Zinc-Ion Battery Containing an Oxygen-Deficient Vanadium Oxide Cathode.

Rechargeable aqueous zinc-ion batteries are attractive because of their inherent safety, low cost, and high energy density. However, viable cathode materials (such as vanadium oxides) suffer from strong Coulombic ion-lattice interactions with divalent Zn2+ , thereby limiting stability when cycled at a high charge/discharge depth with high capacity. A synthetic strategy is reported for an oxygen-deficient vanadium oxide cathode in which facilitated Zn2+ reaction kinetic enhance capacity and Zn2+ pathways for high reversibility. The benefits for the robust cathode are evident in its performance metrics; the aqueous Zn battery shows an unprecedented stability over 200 cycles with a high specific capacity of approximately 400 mAh g-1 , achieving 95 % utilization of its theoretical capacity, and a long cycle life up to 2 000 cycles at a high cathode utilization efficiency of 67 %. This work opens up a new avenue for synthesis of novel cathode materials with an oxygen-deficient structure for use in advanced batteries.

Binder-Free Centimeter-Long V2O5 Nanofibers on Carbon Cloth as Cathode Material for Zinc-Ion Batteries

Recently, rechargeable aqueous zinc-ion batteries (AZBs) have attracted extensive interest due to their safety, abundance, low cost, and low toxicity. However, aqueous electrolytes require a polymeric binder to prevent dissolution of the active material in addition to its binding properties. This study highlights binder-free, centimeter long, single-crystal, V2O5 nanofibers (BCS-VONF) on carbon cloth, as the cathode material for AZBs synthesized via a simple one-step hydrothermal process. BCS-VONF in 3.0 M Zn(OTf)2 exhibit promising electrochemical performance with excellent capacity retention. Even in the absence of a binder, BCS-VONF were found to be very stable in 3.0 M Zn(OTf)2. They will not yield to the dissolution and detachment of the active material on the current collector. The novel strategy described in this study is an essential step for the development of BCS-VONF on carbon cloth, as a promising cathode material for AZBs.

Energy storage performance of CuO as a cathode material for aqueous zinc ion battery

Rechargeable aqueous zinc ion batteries (ZIBs) with high specific capacity appear promising to meet the increasing demand for low cost and sustainable energy storage devices. Because the investigation of aqueous ZIBs is still in the incipient stage, the exploration of cathode materials with high specific capacity is necessary. Herein, the CuO nanorods were prepared by a simple liquid phase method and for the first time the CuO/Zn system with high and stable voltage platform was established successfully. The discharge platform is at 0.82 V and remains stable throughout the charge and discharge process. The constant current charge-discharge test shows that the CuO/Zn battery within the voltage of 0.4–1.1 V delivers high reversible capacity of 219 mA h g−1 at 0.3 A g−1. The cyclic voltammogram analysis shows that the Zn-ion storage in CuO is a diffusion-controlled kinetic process. Meanwhile, the phase evolution study during the first charge-discharge cycle reveals that the energy storage mechanism of CuO cathode is conversion reaction. The results demonstrate the feasibility of a conversion reaction energy storage mechanism for zinc ion batteries.