In alkaline Zn anodes, the active material is discharged to both aqueous zincate ions and solid ZnO. The mobility of zincate in the electrolyte allows considerable transport of the discharge products, which can form directly on the Zn active material or far from it, effectively relocating material long distances inside the cell. Additionally, ZnO can exist in more than one form, namely type I and type II, which differ in their density and passivating character.¹ This leads to complex compositions of discharged primary Zn anodes and can cause cell failure due to redistribution of Zn in rechargeable cells. Models of Zn anodes are typically designed for continuous discharge,² yet real-world use conditions usually involve intermittent discharge. Therefore, the ability of these models to predict ZnO morphology and distribution for cells used in real-world applications is questionable.

It has been previously reported that when alkaline AA cells are discharged, ZnO forms passivating shells around undischarged Zn cores. At high discharge rates, this passivation of Zn increases in severity and hinders cell performance. Additionally, higher discharge rates increase the non-uniformity of ZnO distribution within the anode, preferentially precipitating ZnO near the separator which impedes hydroxide transport from the cathode to the inner portion of the anode.³ In this work, we analyze cylindrical cells discharged using intermittent profiles that approximate real battery use. We then compare the ZnO distribution to that found after continuous discharge.

Synchrotron X-ray tomography was used to obtain in situ volumetric reconstructions at a spatial resolution of 3 microns. To observe the spatial distribution and morphology of ZnO formation in partially discharged Zn anodes, multiple AAA cells were discharged using distinct protocols. When using a continuous discharge, the reconstructions verified previous findings that core-shell structure is the primary morphology of ZnO and is non-uniformly distributed towards the separator.³ However, a radically different morphology and spatial distribution of ZnO was observed when using an intermittent discharge protocol. Specifically, when providing an 8 hour rest after each hour of discharge, ZnO forms isolated clumps distributed throughout the anode. Using this intermittent discharge protocol avoids passivating active material and potentially enables a higher Zn utilization by minimizing isolation of active material.

References

[1] I. Arise et al 2013 J. Electrochem. Soc. 160 D66

[2] E. J. Podlaha and H. Y. Cheh 1994 J. Electrochem. Soc. 141 15

[3] Quinn C. Horn and Yang Shao-Horn 2003 J. Electrochem. Soc. 150 A652