Rechargeable aqueous zinc-manganese dioxide batteries with high energy and power densities
TL;DR: A high-performance rechargeable zinc-manganese dioxide system with an aqueous mild-acidic zinc triflate electrolyte believed to be promising for large-scale energy storage applications.
Abstract: Although alkaline zinc-manganese dioxide batteries have dominated the primary battery applications, it is challenging to make them rechargeable. Here we report a high-performance rechargeable zinc-manganese dioxide system with an aqueous mild-acidic zinc triflate electrolyte. We demonstrate that the tunnel structured manganese dioxide polymorphs undergo a phase transition to layered zinc-buserite on first discharging, thus allowing subsequent intercalation of zinc cations in the latter structure. Based on this electrode mechanism, we formulate an aqueous zinc/manganese triflate electrolyte that enables the formation of a protective porous manganese oxide layer. The cathode exhibits a high reversible capacity of 225 mAh g−1 and long-term cyclability with 94% capacity retention over 2000 cycles. Remarkably, the pouch zinc-manganese dioxide battery delivers a total energy density of 75.2 Wh kg−1. As a result of the superior battery performance, the high safety of aqueous electrolyte, the facile cell assembly and the cost benefit of the source materials, this zinc-manganese dioxide system is believed to be promising for large-scale energy storage applications. The development of rechargeable aqueous zinc batteries are challenging but promising for energy storage applications. With a mild-acidic triflate electrolyte, here the authors show a high-performance Zn-MnO2 battery in which the MnO2 cathode undergoes Zn2+ (de)intercalation.
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1,436 citations
TL;DR: In this paper, a review of recent advances in rechargeable aqueous zinc-ion batteries (ZIBs) is presented, highlighting the design of a highly reversible Zn anode, optimization of the electrolyte, and a wide range of cathode materials and their energy storage mechanisms.
Abstract: Although current high-energy-density lithium-ion batteries (LIBs) have taken over the commercial rechargeable battery market, increasing concerns about limited lithium resources, high cost, and insecurity of organic electrolyte scale-up limit their further development. Rechargeable aqueous zinc-ion batteries (ZIBs), an alternative battery chemistry, have paved the way not only for realizing environmentally benign and safe energy storage devices but also for reducing the manufacturing costs of next-generation batteries. This Review underscores recent advances in aqueous ZIBs; these include the design of a highly reversible Zn anode, optimization of the electrolyte, and a wide range of cathode materials and their energy storage mechanisms. We also present recent advanced techniques that aim at overcoming the current issues in aqueous ZIB systems. This Review on the future perspectives and research directions will provide a guide for future aqueous ZIB study.
1,370 citations
TL;DR: In this article, the authors discuss how to pave the way for developing rechargeable aqueous zinc-ion batteries (ZIBs), including an analysis of the problems encountered in both cathode/anode materials and electrolyte optimization.
Abstract: Zinc-ion batteries built on water-based electrolytes featuring compelling price-points, competitive performance, and enhanced safety represent advanced energy storage chemistry as a promising alternative to current lithium-ion battery systems. Attempts to develop rechargeable aqueous zinc-ion batteries (ZIBs) can be traced to as early as the 1980s; however, since 2015, the research activity in this field has surged throughout the world. Despite the achievements made in exploring electrode materials so far, significant challenges remain at the material level and even on the whole aqueous ZIBs system, leading to the failure of ZIBs to meet commercial requirements. This review aims to discuss how to pave the way for developing aqueous ZIBs. The current research efforts related to aqueous ZIBs electrode materials and electrolytes are summarized, including an analysis of the problems encountered in both cathode/anode materials and electrolyte optimization. Some concerns and feasible solutions for achieving practical aqueous ZIBs are discussed in detail. We would like to point out that merely improving the electrode materials is not enough; synergistic optimization strategies toward the whole battery system are also deeply needed. Finally, some perspectives are provided on the subsequent optimization design for further research efforts in the aqueous ZIB field.
1,033 citations
TL;DR: A design with sodium vanadate hydrate as cathode is shown, allowing simultaneous proton and zinc-ion insertion/extraction and enhanced performance and the quasi-solid-state zinc/sodium vanadates hydrate battery is a good candidate for flexible energy storage device.
Abstract: Rechargeable aqueous zinc-ion batteries are promising energy storage devices due to their high safety and low cost. However, they remain in their infancy because of the limited choice of positive electrodes with high capacity and satisfactory cycling performance. Furthermore, their energy storage mechanisms are not well established yet. Here we report a highly reversible zinc/sodium vanadate system, where sodium vanadate hydrate nanobelts serve as positive electrode and zinc sulfate aqueous solution with sodium sulfate additive is used as electrolyte. Different from conventional energy release/storage in zinc-ion batteries with only zinc-ion insertion/extraction, zinc/sodium vanadate hydrate batteries possess a simultaneous proton, and zinc-ion insertion/extraction process that is mainly responsible for their excellent performance, such as a high reversible capacity of 380 mAh g–1 and capacity retention of 82% over 1000 cycles. Moreover, the quasi-solid-state zinc/sodium vanadate hydrate battery is also a good candidate for flexible energy storage device. Rechargeable zinc-ion batteries are promising energy storage devices but suffer from the limited choice of positive electrodes. Here Niu and co-workers show a design with sodium vanadate hydrate as cathode, allowing simultaneous proton and zinc-ion insertion/extraction and enhanced performance.
1,010 citations
TL;DR: Structurally reinforced polyaniline-intercalated MnO2 nanolayers that boost performance by eliminating phase transformation are reported, which sheds light on the design of advanced cathodes for aqueous zinc-ion batteries.
Abstract: Rechargeable zinc-manganese dioxide batteries that use mild aqueous electrolytes are attracting extensive attention due to high energy density and environmental friendliness. Unfortunately, manganese dioxide suffers from substantial phase changes (e.g., from initial α-, β-, or γ-phase to a layered structure and subsequent structural collapse) during cycling, leading to very poor stability at high charge/discharge depth. Herein, cyclability is improved by the design of a polyaniline-intercalated layered manganese dioxide, in which the polymer-strengthened layered structure and nanoscale size of manganese dioxide serves to eliminate phase changes and facilitate charge storage. Accordingly, an unprecedented stability of 200 cycles with at a high capacity of 280 mA h g-1 (i.e., 90% utilization of the theoretical capacity of manganese dioxide) is achieved, as well as a long-term stability of 5000 cycles at a utilization of 40%. The encouraging performance sheds light on the design of advanced cathodes for aqueous zinc-ion batteries.
906 citations
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TL;DR: Researchers must find a sustainable way of providing the power their modern lifestyles demand to ensure the continued existence of clean energy sources.
Abstract: Researchers must find a sustainable way of providing the power our modern lifestyles demand.
15,980 citations
"Rechargeable aqueous zinc-manganese..." refers background in this paper
...Based on the above results, we propose three merits of the Mn2+ electrolyte additive for the Zn-MnO2 battery: (1) accommodating and compensating Mn2+ dissolution from the electrode, (2) improving initial Coulombic efficiency and ionic conductivity of the electrolyte and (3) generating a uniform porous nanostructured MnOx film on the cathode surface, which helps to maintain the electrode integrity and favor charge transfer....
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TL;DR: Batteries, fuel cells and supercapacitors belong to the same family of energy conversion devices and are needed to service the wide energy requirements of various devices and systems.
Abstract: Electrochemical energy conversion devices are pervasive in our daily lives. Batteries, fuel cells and supercapacitors belong to the same family of energy conversion devices. They are all based on the fundamentals of electrochemical thermodynamics and kinetics. All three are needed to service the wide energy requirements of various devices and systems. Neither batteries, fuel cells nor electrochemical capacitors, by themselves, can serve all applications.
6,230 citations
4,311 citations
TL;DR: A review of post-lithium-ion batteries is presented in this paper with a focus on their operating principles, advantages and the challenges that they face, and the volumetric energy density of each battery is examined using a commercial pouch-cell configuration.
Abstract: Energy density is the main property of rechargeable batteries that has driven the entire technology forward in past decades. Lithium-ion batteries (LIBs) now surpass other, previously competitive battery types (for example, lead–acid and nickel metal hydride) but still require extensive further improvement to, in particular, extend the operation hours of mobile IT devices and the driving mileages of all-electric vehicles. In this Review, we present a critical overview of a wide range of post-LIB materials and systems that could have a pivotal role in meeting such demands. We divide battery systems into two categories: near-term and long-term technologies. To provide a realistic and balanced perspective, we describe the operating principles and remaining issues of each post-LIB technology, and also evaluate these materials under commercial cell configurations. Post-lithium-ion batteries are reviewed with a focus on their operating principles, advantages and the challenges that they face. The volumetric energy density of each battery is examined using a commercial pouch-cell configuration to evaluate its practical significance and identify appropriate research directions.
3,314 citations
"Rechargeable aqueous zinc-manganese..." refers background in this paper
...Based on the above results, we propose three merits of the Mn2+ electrolyte additive for the Zn-MnO2 battery: (1) accommodating and compensating Mn2+ dissolution from the electrode, (2) improving initial Coulombic efficiency and ionic conductivity of the electrolyte and (3) generating a uniform porous nanostructured MnOx film on the cathode surface, which helps to maintain the electrode integrity and favor charge transfer....
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TL;DR: A highly concentrated aqueous electrolyte whose window was expanded to ~3.0 volts with the formation of an electrode-electrolyte interphase, which could potentially be replaced with a safer aQueous alternative to lithium-ion batteries.
Abstract: Lithium-ion batteries raise safety, environmental, and cost concerns, which mostly arise from their nonaqueous electrolytes. The use of aqueous alternatives is limited by their narrow electrochemical stability window (1.23 volts), which sets an intrinsic limit on the practical voltage and energy output. We report a highly concentrated aqueous electrolyte whose window was expanded to ~3.0 volts with the formation of an electrode-electrolyte interphase. A full lithium-ion battery of 2.3 volts using such an aqueous electrolyte was demonstrated to cycle up to 1000 times, with nearly 100% coulombic efficiency at both low (0.15 C) and high (4.5 C) discharge and charge rates.
2,229 citations