Monitoring of Energy Storage Mechanism of Zn/Meso-MnO2
Battery System Using X-Ray Absorption Fine Structure
Authors: Kim Hansol , Cui Chenglin , Kwon Yelim , Lee Jungho , Kim JI Man 
Published: February 2024

As energy storage systems, LIBs, which are most frequently used, have excellent capacity, power, and long lifespan performance [1]. However, as the reserves of the raw minerals used—lithium and cobalt—are exhausted, prices are escalating. A further issue with LIB is that it heats up to a high temperature during charging, which leads to a string of fire or explosion catastrophes. To solve these safety or cost challenges, various next-generation batteries are being developed, and we are exploring about aqueous zinc ion battery (AZIB), which attracting attention as the next-generation battery due to outstanding safety and cost competitive advantage. Generally, zinc metal acting as an anode, has a high theoretical capacity of 820mAh/g as it is gives two electrons (2e-). Also, because of its sparse reactivity with water and ability to employ water-based electrolytes with strong ion conductivity and low ignition risk, it is particularly advantageous in terms of safety. There have been a variety of cathode materials utilized, such as manganese oxide, vanadium oxide, Prussian blue analogues (PBAs), polyanion compounds, and Chevrel phase compounds [2-4].
Especially, manganese dioxide (MnO2) has been addressed by prior studies that Zn2+ can be inserted into crystal structure because it exhibits several crystal structures (α, β, γ, δ, and λ) with tunnel-type or layer-type structure. Mn4+ ions occupying octahedral holes formed by hexagonal close-packed (hcp) oxide ions compose the fundamental unit of the crystal structure of MnO2 polymorphs. To construct a [MnO6] octahedral unit, each Mn4+ ion is precisely surrounded by six oxygen neighbors, and these units are connected by the edges and/or corners [5]. Understanding the energy storage mechanisms is essential for the one-step evolution of cathode materials for AZIB. However, these polymorphs significantly affect the electrochemical reaction, thus involving complex reaction mechanisms [5-7]. Additionally, it is extremely challenging to research the mechanisms of AZIB since protons (H+) are known to participate in the reaction by acting as charge transfer as well as Zn2+ ions. Therefore, while several efforts are being conducted to unveil the exact reaction mechanism, a mesoporous nanostructured material with a large specific surface area is adopted, which can more precisely grasp the electrochemical reaction studies of electrode/electrolyte surface [8,9].
X-ray absorption fine structure (XAFS) is a powerful technique used for the analysis of nanostructured materials, widely used in the field of battery research [10]. It involves the measurement of the absorption of X-ray by the material, which can provide information about oxidation state, chemical bonding of the materials and the local geometry structure during charge/discharge process. This analysis method gives great insight into the complex energy storage pathway of MnO2 materials with various polymorphs.
Based on this knowledge, we synthesized ordered mesoporous β-MnO2 through nano-casting method by using KIT-6 as hard-template and used it as the cathode active material. As depicted in Figure 1, we performed ex-situ XAFS analysis at the states of charge during 2nd cycle to monitor energy storage mechanisms. The oxidation state changes could be quantitatively estimated by edge energy analysis by comparing the reference MnO2 and Mn2O3 samples. It was also possible to unveil further about the reaction mechanism at each voltage by examining the structural change in the local geometry of [MnO6] unit through a careful analysis of pre-edge region and EXAFS spectra. During discharge process, insertion mechanism, which causes relatively larger distortion in the local geometry compared to conversion mechanism, results in a increment of pre-edge intensity, which opposes the decline in pre-edge intensity due to the reduction of the oxidation state. This fact demonstrates that although H+ conversion could not have a significant effect on pre-edge intensity in the early discharge stage, Zn2+ insertion was the phenomenon responsible for the rise in pre-edge intensity during late discharge stage. In addition, through EXAFS spectra analysis, the irreversible change in corner sharing Mn-Mn bond distance during charge/discharge process could be seen that an irreversible phase transition of MnO2 occurred due to Zn2+ insertion, indicating clue to identify the cause of capacity fading. These findings contribute to further understanding of the reaction mechanisms and capacity fading phenomenon and suggest practical strategies for next-generation zinc-ion batteries.

References

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[10] J. Phys. D: Appl. Phys. 50 (2017) 074001

Figure 1