Zhenzhen Yang

Investigation of fluoroethylene carbonate effects on tin-based lithium-ion battery electrodes.

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.

In situ high-energy synchrotron X-ray diffraction studies and first principles modeling of α-MnO2 electrodes in Li–O2 and Li-ion coin cells

Despite their technological challenges, non-aqueous rechargeable lithium–oxygen cells offer extremely high theoretical energy densities and are therefore attracting much attention in a rapidly emerging area of electrochemical research. Early results have suggested that, among the transition metal oxides, alpha manganese dioxide (α-MnO2) appears to offer electrocatalytic properties that can enhance the electrochemical properties of Li–O2 cells, particularly during the early cycles. In this study, we have investigated the hybrid Li-ion/Li–O2 character of α-MnO2 electrodes in Li–O2 coin cells by in situ high-energy synchrotron X-ray diffraction, and compared the results with conventional Li/α-MnO2 coin cells assembled under argon. Complementary first principles density functional theory calculations have been used to shed light on competing lithium insertion and lithium and oxygen insertion reactions within the α-MnO2 tunnel structure during discharge, relative to lithium peroxide or lithium oxide formation.

Quantification of the Mass and Viscoelasticity of Interfacial Films on Tin Anodes Using EQCM-D

Electrochemical quartz crystal microbalance coupled with dissipation (EQCM-D) is employed to investigate the solid electrolyte interphase (SEI) formation and Li insertion/deinsertion into thin film electrodes of tin. Based on the frequency change we find that the initial SEI formation process is rapid before Li insertion but varies significantly with increasing concentration of the additive fluoroethylene carbonate (FEC) in the electrolyte. The extent of dissipation, which represents the film rigidity, increases with cycle number, reflecting film thickening and softening. Dissipation values are almost twice as large in the baseline electrolyte (1.2 M LiPF6 in 3:7 wt % ethylene carbonate:ethyl methyl carbonate), indicating the film in baseline electrolyte is roughly twice as soft as in the FEC-containing cells. More importantly, we detail how quantitative data about mass, thickness, shear elastic modulus, and shear viscosity in a time-resolved manner can be obtained from the EQCM-D response. These parameters were extracted from the frequency and dissipation results at multiple harmonics using the Sauerbrey and Voigt viscoelastic models. From these modeled results we show the dynamic mass changes for each half cycle. We also demonstrate that different amounts of FEC additive influence the SEI formation behavior and result in differences in the estimated mass, shear modulus and viscosity. After three cycles, the film in baseline electrolyte exhibits a 1.2 times larger mass change compared with the film in the FEC-containing electrolyte. The shear elastic modulus of films formed in the presence of FEC is larger than in the baseline electrolyte at early stages of lithiation. Also with lithiation is a marked increase in film viscosity, which together point to a much stiffer and more homogeneous SEI formed in the presence of FEC.