Investigation on Zinc Ion Storage in Alpha Manganese Dioxide for Zinc Ion Battery by Electrochemical Impedance Spectrum

Abstract

The storage process of Zn 2+ ion into α-MnO 2 has been investigated by electrochemical impedance spectrum. A new phase formation process has been recognized. The equivalent circuit model and the impedance expression have been built up to characterize the storage of Zn 2+ ion into α-MnO 2 . It is found that the storage process of Zn 2+ ions is mainly determined by the phase change. With the decrease of potential, Zn 2+ ions begin to insert into MnO 2 and phase change occurs, which leads to a significant increase on phase change resistance (R T ). We also investigated the relationship between the phase change and the phase angle. It is mathematically calculated that maximum phase angle (| | 0 ) at low frequency domain shows a logarithmic dependence on R T , which is confirmed by the experimental results. By using | | 0 directly from Bode plot, we can easily monitor the phase change and the storage process of zinc ion into MnO 2 .Due to the energy crisis and environmental deterioration, our society seeks renewable energy sources for a sustainable growth of human population and living standards. Solar, wind, water, nuclear, tidal, geothermal energies are now considered as the renewable sources to solve the challenges facing society today. Along with energy production, renewable energy systems need the ability to store energy for reuse on various purposes. The use of electricity generated from these renewable sources requires efficient distributed electrical energy storage by batteries on scales ranging from public utilities to miniaturized portable electronic devices. Batteries, which are playing a key role on the utilization of the renewable energy sources, normally store energy through an electrochemical way. 1 There are several kinds of rechargeable batteries, for example, lithium ion, nickel metal hybrid, nickel cadmium, lead acid batteries, serving as the efficient devices for the energy storage. 2-7 Lithium ion battery is now a rising star to meet the demand of high energy density. The battery chemistry of a lithium ion battery utilizes the migration of lithium ion (Li + ion) between a cathodic lithium metal oxide (for example LiCoO 2 ) and an anodic carbon (for example graphite). 2 Lithium ion running between cathode and anode is nothing but a medium for the electric storage. Despite the high energy density demand, our society also requires the safety, environmentally friendly, and low cost battery to meet the demand of the next generation electric or electrical devices. 8 More recently, the so-called energetic zinc ion chemistry has been proposed by us and a battery named as zinc ion battery has been built up. 9,10 In such a battery, the battery chemistry is based on the migration of Zn 2+ ions between α-MnO 2 cathode and Zn anode within a mild aqueous ZnSO 4 electrolyte. This battery shows a great potential on the applications where both power and energy needs.In our previous works, we found that alpha manganese dioxide (α-MnO 2 ) can store and release zinc ion (Zn 2+ ) fast and reversibly. The storage/relea...

Kinetic Behavior of Manganese Dioxide in Li/MnO2Primary Batteries Investigated Using Electrochemical Impedance Spectroscopy under Nonequilibrium State

“…The first impedance measurements of batteries appear to have been performed by Willihnganz in 1941. 5 Xu et al 6 investigated the process and monitored the phase change of the storage of Zn 2+ ions into α-MnO 2 by EIS. Arnott et al 7 examined the electrochemical and morphological changes that γ-MnO 2 undergoes during reduction in an alkaline manganese dioxide cathode.…”

Reversible Electrochemical Insertion/Extraction of Mg and Li Ions for Orthorhombic Mo9Se11with Cluster Structure

“…Redistribution subject to ECS terms of use (see 18.236.120. 13 Downloaded on 2018-05-12 to IP anisotropic channel character, would not allow filling of a larger part of the vacant sites although the number of them is high in o-Mo 9 Se 11 . 21 On the other hand, in the case of Chevrel compounds, Mo 6 X 8 (X = S, Se), with three-dimensional diffusion channel, 33 it is reported that both Li-and Mg-systems show the similar order capacity comparable with the theoretical capacity 11,12,[17][18][19][20]34,35 deduced from the molecular orbital model, 23 in which extra four electrons per formula unit form closed-shell configuration of bonding orbitals.…”

“…[1][2][3][4] In recent years, an effort for developing new energy storage systems, which use ion-insertion mechanism, is being invested also in nonlithium-ion battery systems, such as sodium-ion, 5,6 potassium-ion 7,8 and multivalent-ion batteries. [9][10][11][12][13][14][15][16] Among them, Mg-ion battery is one of the fascinating battery systems due to its possible low cost and safety, which could be realized by rich resource and moderate reactivity of magnesium. [9][10][11][12] However, in most materials, the strong electrostatic interaction between introduced Mg 2+ and host lattice, which is due to bivalence of Mg 2+ , induces the slow solid state diffusion of Mg-ions within the crystal lattice and hampers reversible electrochemical insertion/extraction of Mg 2+ .…”

Charge storage mechanism of MnO 2 cathodes in Zn/MnO 2 batteries using ionic liquid-based gel polymer electrolytes

“…In addition, MnO 2 is the most widely used cathode, which can produce large discharge capacities, higher than 200 mAh g −1 with a practical potential of 1.3 V [2][3][4]. Until now, charge storage mechanism of MnO 2 has been only investigated in aqueous electrolytes, and two mechanisms have been proposed to explain it [5][6][7].…”

“…Intercalation of divalent cations, such as Mg 2+ and Zn 2+ , into MnO 2 have been recently reported, opening the development of an emerging energy storage system: Zn 2+ or Mg 2+ ion batteries as most viable candidates for replacing Li-ion batteries [2][3][4]8,9]. In this sense, Oh et al have published a series of papers describing the intercalation of Zn 2+ cations into different MnO 2 structures [4,8,9].…”