Zheng Jingxu, Deng Yue, Li Wenzao, Yin Jiefu, West Patrick J, Tang Tian, Tong Xiao, Bock David C, Jin Shuo, Zhao Qing, Garcia-Mendez Regina, Takeuchi Kenneth J, Takeuchi Esther S, Marschilok Amy C, Archer Lynden A
Department of Materials Science and Engineering, Cornell University, Ithaca, NY 14853, USA.
Department of Physics, Massachusetts Institute of Technology, Cambridge, MA 02139, USA.
Sci Adv. 2022 Nov 4;8(44):eabq6321. doi: 10.1126/sciadv.abq6321.
How surface chemistry influences reactions occurring thereupon has been a long-standing question of broad scientific and technological interest. Here, we consider the relation between the surface chemistry at interfaces and the reversibility of electrochemical transformations at rechargeable battery electrodes. Using Zn as a model system, we report that a moderate strength of chemical interaction between the deposit and the substrate-neither too weak nor too strong-enables highest reversibility and stability of the plating/stripping redox processes. Focused ion beam and electron microscopy were used to directly probe the morphology, chemistry, and crystallography of heterointerfaces of distinct natures. Analogous to the empirical Sabatier principle for chemical heterogeneous catalysis, our findings arise from competing interfacial processes. Using full batteries with stringent negative electrode-to-positive electrode capacity (N:P) ratios, we show that such knowledge provides a powerful tool for designing key materials in highly reversible battery systems based on Earth-abundant, low-cost metals such as Zn and Na.
表面化学如何影响发生在其表面的反应，一直是一个具有广泛科学和技术兴趣的长期问题。在此，我们考虑界面处的表面化学与可充电电池电极上电化学转变的可逆性之间的关系。以锌作为模型体系，我们报告称，沉积物与基底之间适度的化学相互作用强度——既不太弱也不太强——能够实现电镀/脱镀氧化还原过程的最高可逆性和稳定性。聚焦离子束和电子显微镜被用于直接探测不同性质异质界面的形态、化学性质和晶体学。类似于化学多相催化的经验性萨巴蒂尔原理，我们的发现源于相互竞争的界面过程。使用具有严格负电极与正电极容量（N:P）比的全电池，我们表明，此类知识为基于锌和钠等储量丰富、成本低廉的金属设计高可逆电池系统中的关键材料提供了有力工具。
