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DOE OSTI · 1847079

Material Failure Mechanisms of Alkaline Zn Rechargeable Conversion Electrodes

D’Ambrose, Michael J.·Turney, Damon E.·Yadav, Gautam G.·Nyce, Michael·Banerjee, Sanjoy
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Abstract

Zinc (Zn) alkaline electrodes hold great importance and promise in the battery technology community, yet their behavior in real-world applications is still poorly understood. Here, we report a study of failure mechanisms and material evolution during cycling of 27 zinc–manganese dioxide (Zn–MnO 2 ) cells wherein the percent utilization of the Zn electroactive material is systematically varied between 1 and 16%. Cell fabrication is kept typical of the prevailing industrial cell design. The cycle life ranges from 2800 to 60, depending inversely on the Zn utilization. In all cases, the Zn material microstructure sheds the polytetrafluoroethylene (PTFE) binder and forms zinc oxide (ZnO) rods, with longer rods formed by lower current per Zn mass. Irreversible side reactions such as the hydrogen evolution reaction (HER), short circuits, or gas crossover cause the Zn anode’s charging efficiency to average 92% (as low as 86%), which in turn causes the baseload of metallic Zn to gradually disappear. Cell failure occurs after the baseload of metallic Zn is exhausted. The total lifetime discharge capacity remains constant near 12 ± 5 Ah/g Zn invariant of Zn utilization, which suggests that the aforementioned processes of Zn microstructural evolution and side-reaction destruction of baseload metallic zinc both progress linearly with cell capacity throughput. Manual reproduction of individual Zn failure mechanisms is performed in 22 fresh cells. Tight packing of the microstructure can lead to poor mass transfer, which causes supersaturation of soluble Zn and finally produces a high overvoltage during discharge. Here, the low charging current density yields poor coulombic efficiency due either to the competitive HER or soft short circuits.

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25 ENERGY STORAGE36 MATERIALS SCIENCEalkalineaqueousbatteryelectrochemical cellselectrodesenergy storagematerialsoxidesrechargeablezinc

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D’Ambrose, Michael J., Turney, Damon E., Yadav, Gautam G., Nyce, Michael, Banerjee, Sanjoy. 2021-04-07. Material Failure Mechanisms of Alkaline Zn Rechargeable Conversion Electrodes. https://doi.org/10.1021/acsaem.0c03144

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