In recent years, Prussian blue analogue (PBA) materials have been widely explored and investigated in energy storage/conversion fields. Herein, the structure/property correlations of PBA materials as host frameworks for various charge‐carrier ions (e.g., Na+, K+, Zn2+, Mg2+, Ca2+, and Al3+) is reviewed, and the optimization strategies to achieve advanced performance of PBA electrodes are highlighted. Prospects for further applications of PBA materials in proton, ammonium‐ion, and multivalent‐ion batteries are summarized, with extra attention given to the selection of anode materials and electrolytes for practical implementation. This work provides a comprehensive understanding of PBA materials, and will serve as a guidance for future research and development of PBA electrodes.
Aqueous zinc (Zn) batteries (AZBs) are widely considered as a promising candidate for next‐generation energy storage owing to their excellent safety features. However, the application of a Zn anode is hindered by severe dendrite formation and side reactions. Herein, an interfacial bridged organic–inorganic hybrid protection layer (Nafion‐Zn‐X) is developed by complexing inorganic Zn‐X zeolite nanoparticles with Nafion, which shifts ion transport from channel transport in Nafion to a hopping mechanism in the organic–inorganic interface. This unique organic–inorganic structure is found to effectively suppress dendrite growth and side reactions of the Zn anode. Consequently, the Zn@Nafion‐Zn‐X composite anode delivers high coulombic efficiency (ca. 97 %), deep Zn plating/stripping (10 mAh cm−2), and long cycle life (over 10 000 cycles). By tackling the intrinsic chemical/electrochemical issues, the proposed strategy provides a versatile remedy for the limited cycle life of the Zn anode.
Aqueous Zn‐MnO2 batteries using mild electrolyte show great potential in large‐scale energy storage (LSES) application, due to high safety and low cost. However, structure collapse of manganese oxides upon cycling caused by the conversion mechanism (e.g., from tunnel to layer structures for α‐, β‐, and γ‐phases) is one of the most urgent issues plaguing its practical applications. Herein, to avoid the phase conversion issue and enhance battery performance, a structurally robust novel phase of manganese oxide MnO2H0.16(H2O)0.27 (MON) nanosheet with thickness of ≈2.5 nm is designed and synthesized as a promising cathode material, in which a nanosheet structure combined with a novel H+/Zn2+ synergistic intercalation mechanism is demonstrated and evidenced. Accordingly, a high‐performance Zn/MON cell is achieved, showing a high energy density of ≈228.5 Wh kg−1, impressive cyclability with capacity retention of 96% at 0.5 C after 300 cycles, as well as exhibiting rate performance of 115.1 mAh g−1 at current rate of 10 C. To the best current knowledge, this H+/Zn2+ synergistic intercalation mechanism is first reported in an aqueous battery system, which opens a new opportunity for development of high‐performance aqueous Zn ion batteries for LSES.
The recent developments in rechargeable aqueous batteries have witnessed a burgeoning interest in the mechanism of proton transport in the cathode materials. Herein, for the first time, we report the Grotthuss proton transport mechanism in α‐MnO2 which features wide [2×2] tunnels. Exemplified by the substitution doping of Ni (≈5 at.%) in α‐MnO2 that increases the energy density of the electrode by ≈25 %, we reveal a close link between the tetragonal‐orthorhombic (TO) distortion of the lattice and the diffusion kinetics of protons in the tunnels. Experimental and theoretical results verify that Ni dopants can exacerbate the TO distortion during discharge, thereby facilitating the hydrogen bond formation in bulk α‐MnO2. The isolated direct hopping mode of proton transport is switched to a facile concerted mode, which involves the formation and concomitant cleavage of O−H bonds in a proton array, namely via Grotthuss proton transport mechanism. Our study provides important insight towards the understanding of proton transport in MnO2 and can serve as a model for the compositional design of cathode materials for rechargeable aqueous batteries.
the past decades, some issues of MnO 2based cathodes still remain due to the low electronic conductivity, [19-21] low utilization of reversible discharge depth, [22,23] sluggish diffusion kinetics, [24-26] and poor structural stability upon cycling, [27-29] which restricts their practical application in the commercial secondary batteries. Taking the Zn-ion batteries as example, the MnO 2 cathode seriously suffer from the above issues, especially the sluggish Zn 2+ diffusion, [30] and structural collapse issue during H + /Zn 2+ intercalation/ extraction cycles. [31-33] Regarding these bottlenecks, researchers have strived to develop strategies that can realize optimizations in capacity, rate, and cycling properties of MnO 2 cathodes, such as surface coating, [34] metal-doping, [35] preintercalation, [36] etc. Among all the strategies, preintercalation strategy provides a basic and effective method for optimizing the structure and electrochemical performance of MnO 2-based cathodes. In recent years, the preintercalation strategy has attracted much attention as an effective approach to enhance the electrochemical performance of cathode materials, including vanadate, [37] manganese oxides, [23] layered LiCoO 2 , [38] etc. Several reviews and prospects have been conducted for MnO 2 materials. Some reviews have mentioned the electrochemical properties and correlated reaction mechanism of MnO 2 materials in aqueous Zn batteries, [29,39,40] and a review by Mai's group offers insights into the rational design of preintercalation electrodes in next-generation rechargeable batteries. [36] However, a review or prospect on the application and mechanism of the preintercalation strategy in MnO 2 materials for nextgeneration batteries is lacking. For MnO 2 electrode materials, many reports on improving the electrochemical properties of materials by applying preintercalation strategy have been emerged in the last 5 years (Table S1 in the Supporting Information). The main feature of the preintercalated MnO 2 materials is that some ions/molecules are preintercalated into the tunnel or interlayer hosts of MnO 2 materials prior to the battery cycling (or during synthesis process). These intercalated guest species, including ions, inorganic/organic molecules, as well as polymers, present electrostatic and physical interactions with the host framework and the inserted carrier ions via chemical bonding or coordination, presenting significant benefiting effect on the inherent structure of hosts and the transport kinetics of carrier ions. Generally, there are several Manganese oxides (MnO 2) are promising cathode materials for various kinds of battery applications, including Li-ion, Na-ion, Mg-ion, and Zn-ion batteries, etc., due to their low-cost and high-capacity. However, the practical application of MnO 2 cathodes has been restricted by some critical issues including low electronic conductivity, low utilization of discharge depth, sluggish diffusion kinetics, and structural instability upon cycling. Preintercalation of ions/molecules ...
Recent years have witnessed a booming interest in grid-scale electrochemical energy storage, where much attention has been paid to the aqueous zinc ion batteries (AZIBs). Among various cathode materials for AZIBs, manganese oxides have risen to prominence due to their high energy density and low cost. However, sluggish reaction kinetics and poor cycling stability dictate against their practical application. Herein, we demonstrate the combined use of defect engineering and interfacial optimization that can simultaneously promote rate capability and cycling stability of MnO2 cathodes. β-MnO2 with abundant oxygen vacancies (VO) and graphene oxide (GO) wrapping is synthesized, in which VO in the bulk accelerate the charge/discharge kinetics while GO on the surfaces inhibits the Mn dissolution. This electrode shows a sustained reversible capacity of ~ 129.6 mAh g−1 even after 2000 cycles at a current rate of 4C, outperforming the state-of-the-art MnO2-based cathodes. The superior performance can be rationalized by the direct interaction between surface VO and the GO coating layer, as well as the regulation of structural evolution of β-MnO2 during cycling. The combinatorial design scheme in this work offers a practical pathway for obtaining high-rate and long-life cathodes for AZIBs.
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