Insights on rational design and energy storage mechanism of Mn-based cathode materials towards high performance aqueous zinc-ion batteries

Aqueous zinc-ion batteries (AZIBs) are regarded as promising electrochemical energy storage devices owing to its low cost, intrinsic safety, abundant zinc reserves, and ideal specific capacity. Compared with other cathode materials, manganese dioxide with high voltage, environmental protection, and high theoretical specific capacity receives considerable attention. However, the problems of structural instability, manganese dissolution, and poor electrical conductivity make the exploration of high-performance manganese dioxide still a great challenge and impede its practical applications. Besides, zinc storage mechanisms involved are complex and somewhat controversial. To address these issues, tremendous efforts, such as surface engineering, heteroatoms doping, defect engineering, electrolyte modification, and some advanced characterization technologies, have been devoted to improving its electrochemical performance and illustrating zinc storage mechanism. In this review, we particularly focus on the classification of manganese dioxide based on crystal structures, zinc ions storage mechanisms, the existing challenges, and corresponding optimization strategies as well as structure–performance relationship. In the final section, the application perspectives of manganese oxide cathode materials in AZIBs are prospected. 

https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/eem2.12575

Recent advances on challenges and strategies of manganese dioxide cathodes for aqueous zinc‐ion batteries

Rechargeable aqueous zinc-ion batteries (ZIBs) have been considered as a promising candidate for the large-scale energy storage device owing to their low cost and high safety. However, the practical application of aqueous ZIBs at low temperature environment is hindered by the freezing aqueous electrolytes, which leads to a sharp drop in ionic conductivity, and thereby a rapid deterioration of battery performance. Herein, a chaotropic salt electrolyte based on low concentration aqueous Zn(ClO4)2 with superior ionic conductivity under low temperature (4.23 mS/cm at −50°C) is reported. The anti-freezing methodology introduced here is completely different from conventional freeze-resistant design of using “water-in-salt” electrolyte, cosolvents, or anti-freezing agent additives strategy. Experimental analysis and molecular dynamics simulations reveal that the as-prepared Zn(ClO4)2 electrolyte possesses faster ionic migration compared with other commonly used Zn-based salts (i.e., Zn(CF3SO3)2 and ZnSO4) electrolyte. It is found that Zn(ClO4)2 electrolyte can suppress the ice crystal construction by forming more hydrogen bonds between solute ClO4− and solvent H2O molecules, thus leading to a superior anti-freezing property. The fabricated ZIBs using this aqueous electrolyte exhibits a dramatically enhanced specific capacity, remarkable rate capability, and great cycling stability over a wide temperature range, from −50 to 25°C. The aqueous ZIBs also exhibit an outstanding energy density of 238.4 Wh/kg without compromising the power density (7.9 kW/kg) under −20°C. Moreover, the assembled aqueous ZIBs can also cycle stably over 1000 cycles at an ultra-low −50°C. The high-safety and cost-effective chaotropic salt electrolyte presented here is a promising strategy for low temperature energy storage application. 

/pdf/an-aqueous-zinc-ion-battery-working-at-50degc-enabled-by-low-r8rhdk58.pdf

An aqueous zinc‐ion battery working at −50°C enabled by low‐concentration perchlorate‐based chaotropic salt electrolyte

Featuring low cost, safety and environmental friendliness, aqueous zinc-ion batteries (AZIBs) have emerged as a promising grid-scale energy storage solution, which, however, are facing challenges especially for their moderate capacity...

Quinoxalinophenazinedione covalent triazine framework for boosted high-performance aqueous zinc-ion battery

Conductive polymer composites cathodes for rechargeable aqueous Zn-ion batteries: A mini-review

High-performance reversible aqueous zinc-ion battery based on iron-doped alpha-manganese dioxide coated by polypyrrole

Abstract Solution growth of single-crystal ferroelectric oxide films has long been pursued for the low-cost development of high-performance electronic and optoelectronic devices. However, the established principles of vapor-phase epitaxy cannot be directly applied to solution epitaxy, as the interactions between the substrates and the grown materials in solution are quite different. Here, we report the successful epitaxy of single-domain ferroelectric oxide films on Nb-doped SrTiO 3 single-crystal substrates by solution reaction at a low temperature of ~200 o C. The epitaxy is mainly driven by an electronic polarization screening effect at the interface between the substrates and the as-grown ferroelectric oxide films, which is realized by the electrons from the doped substrates. Atomic-level characterization reveals a nontrivial polarization gradient throughout the films in a long range up to ~500 nm because of a possible structural transition from the monoclinic phase to the tetragonal phase. This polarization gradient generates an extremely high photovoltaic short-circuit current density of ~2.153 mA/cm 2 and open-circuit voltage of ~1.15 V under 375 nm light illumination with power intensity of 500 mW/cm 2 , corresponding to the highest photoresponsivity of ~4.306×10 −3 A/W among all known ferroelectrics. Our results establish a general low-temperature solution route to produce single-crystal gradient films of ferroelectric oxides and thus open the avenue for their broad applications in self-powered photo-detectors, photovoltaic and optoelectronic devices. 

/pdf/solution-epitaxy-of-polarization-gradient-ferroelectric-2gss48b3.pdf

Solution epitaxy of polarization-gradient ferroelectric oxide films with colossal photovoltaic current

Yttria-stabilized zirconia (YSZ) powder with surface Ni plating has promising application in many fields due to its large surface area, low density and excellent high temperature performance. In this study, YSZ/Ni double-shell powder was fabricated via electroless deposition method, and an active surface kinetic model was developed to tune the surface area and nuclei loading quantitatively. A novel concept, active surface ratio (ASR, the ratio of active deposition surface area to projected area of ceramic powder), is proposed to intrinsically correlate deposition rate with nuclei topology on ceramic surface. The intrinsic relationship between microstructure of metallized ceramic surface and deposition duration was clarified. The active surface kinetic model reveals the correlation between the ASR and instantaneous deposition rate and provides necessary theoretical basis for effective control of ceramic surface modification process by electroless deposition. 

YSZ/Ni double‐shell powder via surface electroless deposition tuned by an active kinetic model

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High-performance reversible aqueous zinc-ion battery based on iron-doped alpha-manganese dioxide coated by polypyrrole

Solution epitaxy of polarization-gradient ferroelectric oxide films with colossal photovoltaic current

YSZ/Ni double‐shell powder via surface electroless deposition tuned by an active kinetic model