Hausmannite Mn ₃ O ₄ as a positive active electrode material for rechargeable aqueous Mn‐oxide/Zn batteries

Abstract

Batteries with manganese (di)oxide/zinc chemistry and aqueous-based electrolytes have the potential to address energy storage demands of stationary applications primarily because of the abundant availability of Zn and Mn-oxides, their intrinsic low cost, and the high specific/volumetric charge capacities. Herein, we report the use of Mn 3 O 4 (hausmannite phase of manganese oxide) as the positive electrode material in a rechargeable near-neutral Mn-oxide/Zn battery configuration. Electrochemical investigations reveal that the hausmannite phase can activate for charge/discharge processes during the first 40 to 50 cycles and then a maximum capacity is obtained. This material shows excellent reversibility (~800 cycles) in keeping more than 65% of its maximum capacity. For the first time, the hausmannite activation mechanism was better understood under near-neutral conditions. By using different characterization techniques (X-ray powder diffraction [XRD], inductively coupled plasmaoptical emission spectrometry [ICP-OES], X-ray photoelectron spectroscopy [XPS], and energy dispersive X-ray spectroscopy [EDS]) formation of Zn-based compounds at the electrode surface was confirmed. One of the compounds formed is the layered double hydroxide (Zn 4 SO 4 [OH] 6 Á 5H 2 O) that forms as a side product. No direct evidence for intercalation of zinc ions was observed. Electrochemical experiments in different aqueous/organic electrolytes has shown that proton intercalation plays a significant role in the charge-storage mechanism, while the activation process itself proceeds, most likely, through the formation of Zn-species at the electrode surface. K E Y W O R D S activation, aqueous battery, energy storage, hausmannite, Mn 3 O 4 , near neutral electrolyte, Zn/ MnO 2 battery 1 | INTRODUCTION According to a recent forecast by the International Energy Agency (IEA), the overall use of renewables in the global energy portfolio will experience a 20% growth during the 2018 to 2023 period and will reach 12.4% by 2023. 1 IEA further forecasts that the decarbonization of the electricity sector, led by solar PV and wind, will see the fastest growth providing almost 30% of power demand in 2023, an increase of 6% from 2017. 1 Nevertheless, renewables, which are enjoying a rapid global growth, require a parallel development of storage

Electrochemical prospects and potential of hausmannite Mn 3 O 4 nanoparticles synthesized through microplasma discharge for supercapacitor applications

“…High yield Mn 3 O 4 NPs are produced by this single step microplasma array method without any pre/post treatments, which requires huge time and energy and toxic chemicals 38 . Stoševski et al 44 reported Hausmannite Mn 3 O 4 NPs as a potential electrode material for rechargeable batteries from their electrochemical analysis.…”

Understanding the Design Principles of Advanced Aqueous Zinc‐Ion Battery Cathodes: From Transport Kinetics to Structural Engineering, and Future Perspectives

“…According to the difference of methodology, the modifying strategies can be summarized into the following five different categories: interlayer intercalation (e.g., cationic intercalated materials, H 2 O intercalated materials, ions and H 2 O co-intercalated materials, and conducting polymer intercalated materials), doping effect, defect engineering, surface coating (e.g., carbon, metal oxide, and conductive polymer), composite formation, as well as the special morphology control (e.g., nanosphere, nanotube, nanofiber, nanosheets, etc.). [158][159][160][161]…”

Freestanding V 5 O 12 · 6H 2 O‐CNTs composite films as cathode for foldable aqueous zinc‐ion batteries

“…Considering these factors, researchers would like to choose aqueous zinc-ion battery (AZIBs), which has the advantages of high abundance, good safety, good flammability resistance and high ionic conductivity. [4][5][6][7][8][9] Nowadays, many cathode materials are being explored, such as manganese oxides, Prussian blue analogs, and vanadium-based compounds. [9][10][11][12][13] Among these potential cathode materials, the layered structure of vanadium oxide has attracted attention as one of the most promising cathode materials in AZIBs owing to vanadium oxide with a larger interlayer spacing for the high charge-radius ratio of Zn 2+ insertion.…”

“…[4][5][6][7][8][9] Nowadays, many cathode materials are being explored, such as manganese oxides, Prussian blue analogs, and vanadium-based compounds. [9][10][11][12][13] Among these potential cathode materials, the layered structure of vanadium oxide has attracted attention as one of the most promising cathode materials in AZIBs owing to vanadium oxide with a larger interlayer spacing for the high charge-radius ratio of Zn 2+ insertion. 14 During the electrode preparation process, the polymer binders, such as polyvinylidene fluoride (PVDF) are usually used to attach active materials and conductive agents to the current collector.…”