Yang Zhenzhen, Gewirth Andrew A, Trahey Lynn
†Chemical Science and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Lemont, Illinois 60439, United States.
‡Department of Chemistry, University of Illinois, 600 South Mathews Avenue, Urbana, Illinois 61801, United States.
ACS Appl Mater Interfaces. 2015 Apr 1;7(12):6557-66. doi: 10.1021/am508593s. Epub 2015 Mar 20.
Electroless plating of tin on copper foil (2-D) and foams (3-D) was used to create carbon- and binder-free thin films for solid electrolyte interphase (SEI) property investigation. When electrochemically cycled vs lithium metal in coin cells, the foam electrodes exhibited better cycling performance than the planar electrodes due to electrode curvature. The effect of the additive/cosolvent fluoroethylene carbonate (FEC) was found to drastically improve the capacity retention and Coulombic efficiency of the cells. The additive amount of 2% FEC is enough to derive the benefits in the cells at a slow (C/9) cycling rate. The interfacial properties of Sn thin film electrodes in electrolyte with/without FEC additive were investigated using in situ electrochemical quartz crystal microbalance with dissipation (EQCM-D). The processes of the decomposition of the electrolyte on the electrode surface and Li alloying/dealloying with Sn were characterized quantitatively by surface mass change at the molecular level. FEC-containing electrolytes deposited less than electrolyte without FEC on the initial reduction sweep, yet increased the overall thickness/mass of SEI after several cyclic voltammetry cycles. EQCM-D studies demonstrate that the mass accumulated per mole of electrons (mpe) was varied in different voltage ranges, which reveals that the reduction products of the electrolyte with/without FEC are different.
通过在铜箔(二维)和泡沫(三维)上进行化学镀锡,制备了无碳且无粘结剂的薄膜,用于研究固体电解质界面(SEI)的性质。在硬币电池中与锂金属进行电化学循环时,由于电极曲率的原因,泡沫电极比平面电极表现出更好的循环性能。研究发现,添加剂/共溶剂氟代碳酸乙烯酯(FEC)能显著提高电池的容量保持率和库仑效率。在缓慢(C/9)循环速率下,2%的FEC添加量足以使电池受益。使用原位电化学石英晶体微天平与耗散技术(EQCM-D)研究了有无FEC添加剂的电解质中Sn薄膜电极的界面性质。通过分子水平的表面质量变化,定量表征了电极表面电解质的分解过程以及Li与Sn的合金化/脱合金化过程。在初始还原扫描时,含FEC的电解质比不含FEC的电解质沉积量少,但经过几个循环伏安循环后,SEI的总厚度/质量增加。EQCM-D研究表明,每摩尔电子积累的质量(mpe)在不同电压范围内有所变化,这表明含FEC和不含FEC的电解质的还原产物不同。