[논문]In-Depth Analysis of Coulombic Efficiency of Zinc-Air Secondary Batteries

Jeong, Jiung; Shin, Heon-Cheol

doi:10.33961/jecst.2019.00339

In-Depth Analysis of Coulombic Efficiency of Zinc-Air Secondary Batteries 원문보기

Journal of electrochemical science and technology, v.11 no.1, 2020년, pp.26 - 32

Jeong, Jiung (School of Materials Science and Engineering, Pusan National University) , Shin, Heon-Cheol (School of Materials Science and Engineering, Pusan National University)

Abstract ▼ AI-Helper

In this study, the side reactions that greatly affect the coulombic efficiency of a zinc-air secondary battery are quantitatively analyzed on the basis of the charging-discharging characteristics, open circuit self-discharge characteristics, and a series of calculations. In particular, the charge amounts consumed by water electrolysis and self-discharge during charging process are separately determined so that the charging efficiency (the amount of charge used in actual charging with respect to the applied charge amount) can be estimated, which would enable systematic understanding of the cause of coulombic efficiency degradation. Using two cells with different charging overvoltages, the validity of the proposed method can be assessed.

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문제 정의

Thus, the suppression of dendritic growth during charging and inhibition of zinc oxide precipitation during discharging have been previously reported to be indispensible for realizing a Zinc-air secondary battery [6,7]. A study of the cell design that improves the above two key issues and separates the contribution of side reactions by applying the method proposed in this study will be subsequently published.
7%, respectively. The results show that the cell design intended to decrease charge loss and increase charging and coulombic efficiencies by reducing the charging overvoltage can be verified by the calculation method presented in this study.

가설 설정

This might be alleviated by the use of more effective additives for the suppression of Zn dendrite growth, like polyethylenimine [18]. (2) Charging curve is neither stable nor consistent in view of overvoltage. This is largely because of the interference by gas bubbles coming from the water electrolysis.
3. The following three factors were considered for calculating the charging efficiency: 1) the charge current is used for the zinc reduction reaction and water decomposition reaction, during which self-discharge from zinc corrosion proceeds simultaneously; 2) the discharge current is used for zinc oxidation, during which selfdischarge from zinc corrosion proceeds simultaneously; and 3) when the open circuit is maintained after charging, only self-discharge from zinc corrosion occurs.

제안 방법

Subsequently, the contribution of each segmented reaction during charging, that is, the amount of charge used for zinc reduction (Q_Zn), the amount of charge lost by water decomposition (Q_WD ), and the amount of charge lost by zinc corrosion (self-discharge; Q_SD ) was calculated by the following procedure. Note that Q_Zn is related to the amount of charge used for actual zinc reduction during charging, excluding Q_SD , i.
This study proposed a simple method to quantify the contribution of side reactions, which have a critical effect on the coulombic efficiency of Zinc-air secondary batteries. From the experimental data and the equations derived in this work, the self-discharge current was determined, and the contribution of main side reactions such as the charge amounts consumed by self-discharge and water electrolysis during charging could be estimated.

성능/효과

From the experimental data and the equations derived in this work, the self-discharge current was determined, and the contribution of main side reactions such as the charge amounts consumed by self-discharge and water electrolysis during charging could be estimated. By applying the proposed method to two cell designs with different charging overvoltages, it was found that the amount of charge consumed by water electrolysis during charging greatly decreased with a reduced charging overvoltage, which resulted in increases in charging and coulombic efficiencies. The method proposed in this study is expected to be used not only for a Zinc-air secondary battery, but also as a simple tool for diagnosing other metal-air batteries with similar reaction mechanisms and interpreting the effects of side reactions.
This study proposed a simple method to quantify the contribution of side reactions, which have a critical effect on the coulombic efficiency of Zinc-air secondary batteries. From the experimental data and the equations derived in this work, the self-discharge current was determined, and the contribution of main side reactions such as the charge amounts consumed by self-discharge and water electrolysis during charging could be estimated. By applying the proposed method to two cell designs with different charging overvoltages, it was found that the amount of charge consumed by water electrolysis during charging greatly decreased with a reduced charging overvoltage, which resulted in increases in charging and coulombic efficiencies.
First, the charge amount used for zinc reduction during charging is actually Q_Zn+Q_SD,ch as mentioned above; however, the charging capacity decreases as the reduced zinc re-oxidizes by self-discharge. Second, the charge capacity in the current design conditions, that is, the contribution of charge amount to zinc reduction (the remaining amount without selfdischarge) is about 28.6% (=Q_Zn /Q_ch). Due to the low charging efficiency, the coulombic efficiency is also very low at 26.

후속연구

By applying the proposed method to two cell designs with different charging overvoltages, it was found that the amount of charge consumed by water electrolysis during charging greatly decreased with a reduced charging overvoltage, which resulted in increases in charging and coulombic efficiencies. The method proposed in this study is expected to be used not only for a Zinc-air secondary battery, but also as a simple tool for diagnosing other metal-air batteries with similar reaction mechanisms and interpreting the effects of side reactions.

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