Aqueous Rechargeable Multivalent Metal‐Ion Batteries: Advances and Challenges

Abstract

and transportation applications requires efficient and revolutionary electrical energy storage devices (ESDs). [2] Among the developed ESDs, rechargeable lead-acid batteries and lithium-ion batteries (LIBs) represent the most mature technologies that are widely used as power supplies in today's portable electronics, transportation, and stationary energy storage applications. [3] However, owing to the inadequate rate of improvement in energy density and cycle life, as well as cost and safety concerns of the two well-established battery technologies, there is an urgent need for energy storage technologies "beyond the lead-acid batteries and LIBs," i.e., alternative advanced battery systems to meet the rapidly growing demand of the emerging markets of electric vehicles and grid energy storage. Therefore, the search for the low cost, environmental-benignity, high energy density with rapid energy storage (high power density), and long-cycle life batteries has become one of the world's top issues. Compared with the state-of-the-art nonaqueous LIB systems, new developing aqueous rechargeable batteries, [4] especially for aqueous rechargeable multivalent metal-ion batteries (ARMMBs) by means of a multi-electron-transfer electrode reaction possess prominent advantages including cost efficiency, absolute safety, environmental benignity, and high capacity and rate capability (Figure 1a). [5] Note that the ARMMBs usually consist of a multivalent-metal anode, an aqueous electrolyte in majority and a cathode for accommodation of the multivalentmetal ions. The working mechanism in the ARMMBs is different from multivalent metal-alkaline batteries (Figure 1b, taking Zn-ion battery and Zn-alkaline battery as examples). [6] Furthermore, the high ionic conductivity of aqueous electrolytes (≈1 and 10 -3 -10 -2 S cm -1 for nonaqueous electrolytes) facilitate high-rate abilities and high-power densities of ARMMBs. [7] Therefore, owing to their better electrochemical performance and advances in the development of nanostructured materials, enormous research interests have turned to ARMMBs, leading to a huge expansion of publications/literatures in the past five years (Figure 1c). However, the insufficient energy density and limited life span of ARMMBs usually hinder their grid-scale applications in the modern society.There have been a couple of reviews published recently on the ongoing hot topic focusing on aqueous rechargeable Aqueous rechargeable multivalent metal-ion batteries (ARMMBs) have a great potential to meet the future demands in the wide spectrum of energy storage applications, ranging from wearables/portables to large-scale stationary energy storage. This is owing to the abundance of the electrode materials, their eco-friendliness, high safety, fast-charging capability, high power density, and long-cycling capability. There has been considerable progress in ARMMBs over the past ten years. However, their rather narrow operating voltage window and insufficient energy density are still the main barriers to their use as a...

Electrochemical reaction behavior of MnS in aqueous zinc ion battery

“…1,2 However, the application of lithium-ion batteries in large-scale energy storage devices is challenged by some intractable problems such as expensive battery components, limited reserves of lithium, and the toxicity and flammability of organic electrolytes. 3,4 The rechargeable aqueous metal ion batteries, which are assembled with aqueous solution electrolyte and earth abundant metal anode (e.g., Zn, Mg, and Al), are being revived due to their advantages of simple and convenient assembly, admirable security, and decent ionic conductivity. [5][6][7] Among them, the rechargeable zinc ion battery has aroused considerable attention due to its admirable safety, cost-effectiveness, moderate redox potential (−0.76 V vs. SHE), and decent theoretical capacity (∼820 mA h g −1 ) of the Zn anode.…”

“…[10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26] Among them, manganese-based compounds are considered as one of the most promising ones due to their competitive advantages of environment-friendliness, costeffectiveness, low toxicity, multiple valence states, and tunable structure/function. 3,4,14,18,27 Manganese oxides have been widely studied as zinc ion battery cathode materials and inspiring progress has been made. 4,14,[16][17][18][28][29][30][31] Most recently, MnS x , which is known as another important manganese-based compounds, has also been introduced in zinc ion batteries.…”

Intercalation Mechanism of the Ammonium Vanadate (NH4V4O10) 3D Decussate Superstructure as the Cathode for High-Performance Aqueous Zinc-Ion Batteries

“…Recently, lithium-ion batteries (LIBs) have acquired vital status in the fields of electric vehicles and electronic facilities owing to their superior power energy density and long life span. Nevertheless, considering the shortage of lithium resources as well as environmental friendliness, the multivalent cation (zinc ion, magnesium ion, and calcium ion) batteries and quasi-solid-state energy storage devices are gradually proposed to alter the LIBs. − In particular, zinc-ion batteries (ZIBs) exhibit unparalleled electrochemical capacity due to their negative redox potential (−0.76 eV vs standard hydrogen electrode) and superior theoretical discharge capacity of 870 mA h g –1 (volume capacity of 5851 mA h cm –3 ) . Additionally, aqueous zinc-ion batteries (AZIBs) with mild aqueous electrolytes possess considerable merits including low cost, nontoxicity, as well as distinguished energy density, which can result in the AZIBs becoming a brilliant energy storage facility to replace LIBs .…”

Regulating the Interlayer Spacing of Vanadium Oxide by In Situ Polyaniline Intercalation Enables an Improved Aqueous Zinc-Ion Storage Performance

“…Developing novel rechargeable battery systems with a high-rate property, high security, low cost, environmental friendliness, and long cycle life possesses important technical significance for the emerging and large-scale energy storage grids. − Although lithium-ion batteries have been applied comprehensively in multiple fields, they still suffer from the scarcity of Li resources and flammability of organic electrolytes. − In recent years, rechargeable aqueous zinc-ion batteries (ZIBs) have attracted great attention owing to their obvious advantages, including high theoretical capacity (820 mA h g –1 ), abundant Zn resources, high safety, environmental friendliness, and low redox voltage (−0.76 V vs standard hydrogen electrode). − At present, polyanionic compounds, manganese oxides, vanadium oxides, and Prussian blue analogues have been proven to effectively store Zn 2+ , − in which vanadium pentoxide (V 2 O 5 ) attracts much attention because of its high theoretical capacity (589 mA h g –1 ), tunable layered spacing, and abundant redox states of vanadium. , However, the Zn 2+ diffusion kinetics of pristine V 2 O 5 is dramatically hindered by its relatively small interlayer spacing, which finally leads to the unsatisfactory cycling stability. In addition, the low electronic conductivity of V 2 O 5 is also not able to allow fast electron/ion transfer, resulting in the undermined utilization of active materials and unsatisfactory power/energy density. − Therefore, a rational strategy should be taken to reinforce the reaction kinetics of the V 2 O 5 cathode.…”