Cen Hongyu, Gao Yijian, He Shasha, Peng Zhuo, Wu Chonggang, Chen Zhenyu
Hubei Provincial Key Laboratory of Green Materials for Light Industry and School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan, Hubei, 430068, China.
Hubei Provincial Key Laboratory of Green Materials for Light Industry and School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan, Hubei, 430068, China.
J Colloid Interface Sci. 2024 Apr;659:160-177. doi: 10.1016/j.jcis.2023.12.142. Epub 2023 Dec 27.
The self-discharge by corrosion of zinc-air batteries (ZABs) will result in the reduced coulombic efficiency and lower energy efficiency. The additives in electrolyte should not only inhibit the occurrence of self-corrosion during battery dormancy, but also achieve a stable cycle of adsorption-desorption during battery operation, improving the durability of discharge cycles. But the former requires strong binding between additives and zinc to form a dense protective film, while the latter requires easy desorption of additives and zinc without affecting discharge power, which is contradictory to balance. In this study, a dynamic combination of additives and zinc, as well as a design of multi-channel strategy for the corresponding protective layer, have been proposed to solve the issues of self-corrosion and discharge cycle stability. Specifically, the surfactant (octylphenol polyoxyethylene ether phosphate (OP-10P)) and 1,10-decanedithiol (DD) have been selected as the combined anti-corrosion additives in ZABs with concentrated alkaline solution. The synergistic inhibition mechanism and the stabilization mechanism in zinc-air full cells have been studied systematically. The results indicated that the combined inhibitors inhibited the self-corrosion of Zn efficiently in the dormancy, and the inhibition efficiency reached 99.9 % at the optimized proportion. OP-10P achieve the preferential adsorption on the zinc surface, and then the chelates of DD with Zn deposit on the outer layer to form the protective film with fine hydrophobic performance. The stability of ZABs in discharge and charging cycles has been improved owing to the multilayer adsorption film on zinc surface, which retains ion transport channels with the homogeneously pores to weaken the dendrites and side reactions during galvanostatic cycles. A probable model on zinc surface was established to discuss the actual working mechanism.
锌空气电池(ZABs)因腐蚀导致的自放电会降低库仑效率和能量效率。电解质中的添加剂不仅应在电池休眠期间抑制自腐蚀的发生,还应在电池运行期间实现稳定的吸附 - 解吸循环,提高放电循环的耐久性。但前者要求添加剂与锌之间有强结合力以形成致密的保护膜,而后者要求添加剂与锌易于解吸且不影响放电功率,这在平衡上是相互矛盾的。在本研究中,提出了添加剂与锌的动态组合以及相应保护层的多通道策略设计,以解决自腐蚀和放电循环稳定性问题。具体而言,在浓碱性溶液的锌空气电池中,选择了表面活性剂(辛基酚聚氧乙烯醚磷酸酯(OP - 10P))和1,10 - 癸二硫醇(DD)作为复合防腐添加剂。系统地研究了锌空气全电池中的协同抑制机制和稳定机制。结果表明,复合抑制剂在休眠状态下能有效抑制锌的自腐蚀,在优化比例下抑制效率达到99.9%。OP - 10P优先吸附在锌表面,然后DD与锌的螯合物沉积在外层形成具有良好疏水性能的保护膜。由于锌表面的多层吸附膜,锌空气电池在充放电循环中的稳定性得到提高,该吸附膜保留了具有均匀孔隙的离子传输通道,以减弱恒电流循环期间的枝晶和副反应。建立了一个关于锌表面的可能模型来讨论实际工作机制。