Dlugatch Ben, Mohankumar Meera, Attias Ran, Krishna Balasubramoniam Murali, Elias Yuval, Gofer Yosef, Zitoun David, Aurbach Doron
Department of Chemistry, Bar-Ilan University, Ramat Gan 5290002, Israel.
Department of Chemistry, CMS College, Kottayam 686001, Kerala, India.
ACS Appl Mater Interfaces. 2021 Nov 24;13(46):54894-54905. doi: 10.1021/acsami.1c13419. Epub 2021 Nov 15.
One of the greatest challenges toward rechargeable magnesium batteries is the development of noncorrosive electrolyte solutions with high anodic stability that can support reversible Mg deposition/dissolution. In the last few years, magnesium electrolyte solutions based on Cl-free fluorinated alkoxyborates were investigated for Mg batteries due to their high anodic stability and ionic conductivity and the possibility of reversible deposition/dissolution in ethereal solvents. Here, the electrochemical performance of Mg[B(hexafluoroisopropanol)]/dimethoxyethane (Mg[B(HFIP)]/DME) solutions was examined. These electrolyte solutions require a special "conditioning" pretreatment that removes undesirable active moieties. Such a process was developed and explored, and basic scientific issues related to the mechanism by which it affects Mg deposition/dissolution were addressed. The chemical changes that occur during the conditioning process were examined. Mg[B(HFIP)]/DME solutions were found to enable reversible Mg deposition, albeit with a relatively low Coulombic efficiency of 95% during the first cycles. Prolonged deposition/dissolution cycling tests demonstrate a stable behavior of magnesium electrodes. Overall, this system presents a reasonable electrolyte solution and can serve as a basis for future efforts to develop chlorine-free alternatives for secondary magnesium batteries. It is clear that such a conditioning process is mandatory, as it removes reactive contaminants that lead to unavoidable passivation and deactivation of Mg electrodes from the solution.
可充电镁电池面临的最大挑战之一是开发具有高阳极稳定性的无腐蚀性电解质溶液,以支持镁的可逆沉积/溶解。在过去几年中,基于无氯氟代烷氧基硼酸盐的镁电解质溶液因其高阳极稳定性、离子导电性以及在醚类溶剂中可逆沉积/溶解的可能性而被用于镁电池研究。在此,对Mg[B(六氟异丙醇)]/二甲氧基乙烷(Mg[B(HFIP)]/DME)溶液的电化学性能进行了研究。这些电解质溶液需要特殊的“预处理”来去除不良活性部分。开发并探索了这样一个过程,并解决了与其影响镁沉积/溶解机制相关的基础科学问题。研究了预处理过程中发生的化学变化。发现Mg[B(HFIP)]/DME溶液能够实现镁的可逆沉积,尽管在最初的循环中库仑效率相对较低,为95%。长时间的沉积/溶解循环测试表明镁电极具有稳定的性能。总体而言,该体系提供了一种合理的电解质溶液,可为未来开发二次镁电池无氯替代品的努力奠定基础。很明显,这样的预处理过程是必不可少的,因为它能从溶液中去除导致镁电极不可避免地钝化和失活的活性污染物。