Kwon Ki Young, Jo Tae Hyeon, Kim Ji Su, Hasan Fuead, Yoo Hyun Deog
Department of Chemistry and Chemical Institute for Functional Materials, Pusan National University, Busan 46241, Republic of Korea.
ACS Appl Mater Interfaces. 2020 Sep 23;12(38):42612-42621. doi: 10.1021/acsami.0c06560. Epub 2020 Sep 9.
Research studies on zinc metal-based batteries have attracted considerable attention as a candidate for post-lithium-ion batteries. Zinc is one of the few metal anodes that is compatible with aqueous and non-aqueous electrolytes, providing a large theoretical capacity of 820 mAh g. However, in aqueous electrolytes, the zinc metal anode suffers from hydrogen evolution reaction (HER), by which zinc is irreversibly consumed or corroded continually. Exact estimation of the corrosion rate has been a challenge in the development of Zn-based batteries. Measurement of the corrosion rate by conventional Tafel analysis meets serious problems because the cathodic current reflects deposition of Zn metal as well as HER, inhibiting exact measurement of the corrosion rate. Herein, we developed a chronocoulometric "deposition-rest-dissolution" method to quantify the corrosion rate without such interference from the deposition of Zn. The method was successfully applied to the quantification of the rate of chemical corrosion of Zn in aqueous electrolytes with various pH and concentration values. The "deposition-rest-dissolution" method and electrochemical impedance spectroscopy confirmed that saturated ZnSO (ca. 3.2 M) + 0.075 M LiSO delivers the lowest corrosion rate compared to the other electrolytes, probably because the activity of water in such a concentrated electrolyte is low enough to suppress the kinetics of HER. Moreover, this method can be generally applied to determine the rate of chemical corrosion on various metal electrodes.
基于锌金属的电池研究作为锂离子电池的候选者已引起了相当大的关注。锌是少数几种与水性和非水性电解质兼容的金属负极之一,其理论容量高达820 mAh g。然而,在水性电解质中,锌金属负极会发生析氢反应(HER),导致锌不断被不可逆地消耗或腐蚀。准确估算腐蚀速率一直是锌基电池开发过程中的一项挑战。采用传统的塔菲尔分析来测量腐蚀速率会遇到严重问题,因为阴极电流既反映了锌金属的沉积,也反映了析氢反应,从而阻碍了对腐蚀速率的准确测量。在此,我们开发了一种计时电量法“沉积-静置-溶解”方法,以在不受锌沉积干扰的情况下量化腐蚀速率。该方法成功应用于量化不同pH值和浓度的水性电解质中锌的化学腐蚀速率。“沉积-静置-溶解”方法和电化学阻抗谱证实,与其他电解质相比,饱和硫酸锌(约3.2 M)+ 0.075 M硫酸锂的腐蚀速率最低,这可能是因为在这种浓电解质中水的活性足够低,从而抑制了析氢反应的动力学。此外,该方法通常可用于确定各种金属电极上的化学腐蚀速率。