Manganese oxide catalysts for secondary zinc air batteries: from electrocatalytic activity to bifunctional air electrode performance (original) (raw)
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Energy Materials, 2022
A major challenge in developing zinc-air batteries (ZABs) is to exploit suitable cathodes to efficiently accelerate the key electrocatalytic processes involved. Herein, a bifunctional oxygen catalytic self-supported MnO2-based electrode is designed that displays superior oxygen reduction and evolution reaction performance over noble metal electrodes with a total overpotential of 0.69 V. In addition, the as-synthesized NiCo2O4@MnO2/carbon nanotube (CNT)-Ni foam self-supported electrode can be directly used as an oxygen electrode without externally adding carbon or a binder and shows reasonable battery performance with a high peak power density of 226 mW cm-2 and a long-term charge-discharge cycling lifetime (5 mA for 160 h). As expected, the rapid oxygen catalytic intrinsic kinetics and high battery performance of the NiCo2O4@MnO2/CNTs-Ni foam electrode originates from the unique three-dimensional hierarchical structure, which effectively promotes mass transfer. Furthermore, the CNTs combined with Ni foam form a unique “meridian” conductive structure that enables rapid electron conduction. Finally, the abundant Mn3+ active sites activated by bimetallic ions shorten the oxygen catalytic reaction distance between the active sites and reactant and reduce the surface activity of MnO2 for the O, OH, and OOH species. This work not only offers a high-performance bifunctional self-supported electrode for ZABs but also opens new insights into the activation of Mn-based electrodes.
Electrochimica Acta, 2019
Electrically rechargeable zinc-air batteries have gained great attention in recent years due to their capacity to provide high energy density. The electrolyte has played a key role in the advancement of this technology and recently, aqueous chloride-based electrolytes have been demonstrated as a possible alternative to the traditional alkaline system. This study investigates, for the first time, the selection of an optimal bifunctional air electrode (BAE) formulation in two aqueous chloride-based electrolytes (pH4 and pH8) for zinc-air batteries. The effect of different Mn x O y-based catalysts and carbon materials with different electrode formulations are electrochemically analyzed in the two electrolytic systems. The BAE formulation containing 20 wt.% γ-MnO 2 , 70 wt.% carbon nanotubes (CNT) and 10 wt.% PTFE demonstrated the lowest overpotential, among all studied formulations, in both electrolytes. The cycling tests carried out using the selected electrode formulation, at both pH4 and pH8, reveal stable discharge-charge cycling over 400 hours with an overpotential lower than 1.1V. Moreover, the absence of manganese dissolution for the pH8 electrolyte is confirmed by ICP analysis, which overcomes the issue concerning the dissolution of manganese in more acidic media. Contrary to what is stated in conventional alkaline zinc-air batteries, where α-MnO 2 is the most promising catalyst, this study highlights the potential of γ-MnO 2-based BAEs when using aqueous chloride-based electrolyte.
Manganese-based bifunctional electrocatalysts for zinc-air batteries
Current Opinion in Electrochemistry, 2020
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Electrochimica Acta, 2012
A composite bifunctional catalyst (MnO 2-NCNT) was prepared from manganese dioxide (MnO 2) nanotubes and nitrogen-doped carbon nanotubes (NCNT) for the purpose of oxygen reduction (ORR) and evolution (OER) catalysis in the rechargeable zinc-air battery. From the half cell test, the MnO 2-NCNT composite illustrated excellent activities towards ORR and OER in alkaline conditions. Based on the battery test, the composite catalyst displayed outstanding discharge and charge performance while maintaining good stability. In both cases, the marked performance improvements from MnO 2-NCNT compared favourably to the NCNT and MnO 2 , which are the constituents of the composite. In particular, MnO 2-NCNT exhibited improved half wave potential by 220 mV compared to MnO 2 and much superior OER stability compared to NCNT based on the rotating ring disk voltammetry results. According to battery test, MnO 2-NCNT decrease the battery resistance by 34% and concurrently improved the durability, discharge and charge performance in comparison to the MnO 2 nanotubes.
Journal of Materials Chemistry A, 2017
Aqueous Zn-ion batteries (ZIBs) have emerged as promising and eco-friendly next-generation energy storage systems to substitute lithium-ion batteries. Therefore, discovering new electrode materials for ZIBs with high performance and unraveling their electrochemical reactions during Zn-ion insertion/ extraction are of great interest. Here, we present, for the first time, tunnel-type b-MnO 2 nanorods with exposed (101) planes, prepared via a facile microwave-assisted hydrothermal synthesis within only 10 min, for use as a high performance cathode for ZIBs. In contrast to its bulk counterpart, which showed no electrochemical reactivity, the present b-MnO 2 nanorod electrode exhibited a high discharge capacity of 270 mA h g À1 at 100 mA g À1 , high rate capability (123 and 86 mA h g À1 at 528 and 1056 mA g À1 , respectively), and long cycling stability (75% capacity retention with 100% coulombic efficiency at 200 mA g À1) over 200 cycles. The Zn-ion storage mechanism of the cathode was also unraveled using in situ synchrotron, ex situ X-ray diffraction, ex situ X-ray photoelectron spectroscopy, and ex situ X-ray absorption spectroscopy. Our present study indicates that Zn intercalation occurred via a combination of solid solution and conversion reactions. During initial cycles, the b-MnO 2 cathode was able to maintain its structure; however, after prolonged cycles, it transformed into a spinel structure. The present results challenge the common views on the b-MnO 2 electrode and pave the way for the further development of ZIBs as cost-effective and environmentally friendly next-generation energy storage systems.
Preliminary study of alkaline single flowing Zn–O2 battery
Electrochemistry Communications, 2009
A new single flow alkaline battery, Zn-K 2 [Zn(OH)] 4 -O 2 battery, in which electrodeposited zinc is employed as an negative electrode and the oxygen in atmosphere as an high-capacity positive electrode active material is developed. The working process of the battery only depends on the circulation of a single electrolyte solution with assistance of a single pump and no cationic membrane is needed. The newly designed dual catalytical layers of composite oxygen electrode employs nano-structured Ni(OH) 2 and the electrolytic manganese dioxide doped with NaBiO 3 as two types of novel highly-efficient catalysts for oxygen evolution and reduction process, respectively. Cell (grade 1000 mAh) test results show that high efficiency is achieved with an average coulombic efficiency of 97.4% and an energy efficiency of 72.2% in 150 cycles.
Recent Progress in Extending the Cycle‐Life of Secondary Zn‐Air Batteries
ChemNanoMat, 2021
Secondary Zn‐air batteries with stable voltage and long cycle‐life are of immediate interest to meet global energy storage needs at various scales. Although primary Zn‐air batteries have been widely used since the early 1930s, large‐scale development of electrically rechargeable variants has not been fully realized due to their short cycle‐life. In this work, we review some of the most recent and effective strategies to extend the cycle‐life of Zn‐air batteries. Firstly, diverse degradation routes in Zn‐air batteries will be discussed, linking commonly observed failure modes with the possible mechanisms and root causes. Next, we evaluate the most recent and effective strategies aimed at tackling individual or multiple of these degradation routes. Both aspects of cell architecture design and materials engineering of the electrodes and the electrolytes will be thoroughly covered. Finally, we offer our perspective on how the cycle‐life of Zn‐air batteries can be extended with concerted...
iScience, 2020
Rechargeable aqueous Zn/manganese dioxide (Zn/MnO 2) batteries are attractive energy storage technology owing to their merits of low cost, high safety, and environmental friendliness. However, the b-MnO 2 cathode is still plagued by the sluggish ion insertion kinetics due to the relatively narrow tunneled pathway. Furthermore, the energy storage mechanism is under debate as well. Here, b-MnO 2 cathode with enhanced ion insertion kinetics is introduced by the efficient oxygen defect engineering strategy. Density functional theory computations show that the b-MnO 2 host structure is more likely for H + insertion rather than Zn 2+ , and the introduction of oxygen defects will facilitate the insertion of H + into b-MnO 2. This theoretical conjecture is confirmed by the capacity of 302 mA h g À1 and capacity retention of 94% after 300 cycles in the assembled aqueous Zn/ b-MnO 2 cell. These results highlight the potentials of defect engineering as a strategy of improving the electrochemical performance of b-MnO 2 in aqueous rechargeable batteries.
2024
Safety issues of energy storage devices in daily life are receiving growing attention, together with resources and environmental concerns. Aqueous zinc ion batteries (AZIBs) have emerged as promising alternatives for extensive energy storage due to their ultra-high capacity, safety, and eco-friendliness. Manganese-based compounds are key to the functioning of AZIBs as the cathode materials thanks to their high operating voltage, substantial charge storage capacity, and eco-friendly characteristics. Despite these advantages, the development of high-performance Mn-based cathodes still faces the critical challenges of structural instability, manganese dissolution, and the relatively low conductivity. Primarily, the charge storage mechanism of manganese-based AZIBs is complex and subject to debate. In view of the above, this review focuses on the mostly investigated MnO2-based cathodes and comprehensively outlines the charge storage mechanisms of MnO2-based AZIBs. Current optimization strategies are systematically summarized and discussed. At last, the perspectives on elucidating advancing MnO2 cathodes are provided from the mechanistic, synthetic, and application-oriented aspects.
Studies on the oxygen reduction catalyst for zinc–air battery electrode
Journal of Power Sources, 2003
In this paper, perovskite type La 0.6 Ca 0.4 CoO 3 as a catalyst of oxygen reduction was prepared, and the structure and performance of the catalysts was examined by means of IR, X-ray diffraction (XRD), and thermogravimetric (TG). Mixed catalysts doped, some metal oxides were put also used. The cathodic polarization curves for oxygen reduction on various catalytic electrodes were measured by linear sweep voltammetry (LSV). A Zn-air battery was made with various catalysts for oxygen reduction, and the performance of the battery was measured with a BS-9300SM rechargeable battery charge/discharge device. The results showed that the perovskite type catalyst (La 0.6 Ca 0.4 CoO 3 ) doped with metal oxide is an excellent catalyst for the zinc-air battery, and can effectively stimulate the reduction of oxygen and improve the properties of zinc-air batteries, such as discharge capacity, etc.