Characterizing Distribution and Morphology of ZnO Discharge Products in Commercial Alkaline Zn-MnO2 Batteries

Abstract

During the discharge of alkaline Zn-MnO2 batteries, the dissolution of Zn particles in the anode saturate the electrolyte with zincate, prompting the formation of solid ZnO. Zincate is highly mobile in the electrolyte, giving rise to complex spatial distributions and morphologies of ZnO discharge products. The passivating behavior of ZnO is dependent on its distribution and morphology, as the active Zn particles within the anode must maintain a connection with the electronic network, while also having access to hydroxide ions from the electrolyte.1 Therefore, characterizing the factors that impact ZnO formation is critical to understanding how battery performance is impacted.2 Past attempts to model these batteries fail to adequately predict the behavior of Zn anodes under discharge conditions aimed at simulating real-world use cases.3 This work seeks to better characterize the behavior of Zn anodes in an effort to improve modeling capabilities based on experimental results.4 High resolution synchrotron CT was used to create in situ volumetric reconstructions of anodes from commercial AA and AAA batteries to determine ZnO morphology and radial distribution at various discharge conditions. Through a novel segmentation algorithm, quantitative data show a shift in ZnO radial distribution and microporosity depending on the rate and depth at which the anodes were discharged. High rate discharge leads to ZnO formation preferentially near the separator with a lower microporosity, increasing its passivating characteristics. Microporosity calculations show the discharge products form in two types, namely type I ZnO and ZnO hydrate. The latter type had only ever been reported on planar electrodes, yet it has a significant presence in commercial alkaline batteries discharged under certain conditions.4,5 In addition to a decreased microporosity, the morphology of ZnO also showed increased passivating characteristics when discharging using a continuous protocol. Shells of ZnO form around undischarged Zn cores during a continuous discharge, restricting hydroxide transport to the Zn surface and potentially isolating the core from the electronically conductive Zn network. When using a pulsed discharge protocol, ZnO formed distributed regions of microporous ZnO not adhered to undischarged Zn surfaces, leaving the remaining Zn in good contact with the electrolyte. Developing a more robust understanding of the factors that impact ZnO formation will enable more advanced models to be created. Acknowledgements This research was supported by funding from Energizer Holdings, Inc. We acknowledge collaborators Xiaotong Chadderdon, Matthew Wendling, Andrew Chihpin Chuang, and John Okasinski. This research also used resources of the Advanced Photon Source beamline 6-BM, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357.