RESUMO
A trace amount of water in an electrolyte is one of the factors detrimental to the electrochemical performance of silicon (Si)-based lithium-ion batteries that adversely affect the formation and evolution of the solid electrolyte interphase (SEI) on Si-based anodes and change its properties. Thus far, a lack of fundamental and mechanistic understanding of SEI formation, evolution, and properties in the presence of water has inhibited efforts to stabilize the SEI for improved electrochemical performance. Thus, we investigated the SEI formed in a Gen2 electrolyte (1.2 M LiPF6 in ethylene carbonate/ethyl methyl carbonate, 3:7 wt %, water content: <10 ppm) with and without additional water (50 ppm) at varying potentials (1.0, 0.5, 0.2, and 0.01 V vs Li/Li+). The impact of additional water on the morphological, (electro)chemical, and structural properties of SEI was studied using microscopic (atomic force microscopy and scanning spreading resistance microscopy) and spectroscopic (X-ray photoelectron spectroscopy, attenuated total reflection Fourier-transform infrared spectroscopy, and time-of-flight secondary ion mass spectrometry) techniques. The SEI exhibits both potential- and water concentration-dependent trends in its morphology and chemical composition. The presence of additional water in the electrolyte causes parasitic reactions, which onset at â¼1.0 V, resulting in a reduction of electrolyte components and result in the formation of an insulating, fluorophosphate-rich SEI. In addition, hydrolysis of LiPF6 creates hydrofluoric acid, which reacts with the surface oxide layer on the Si electrode, leading to a pitted and inhomogeneous SEI structure.
RESUMO
A stable solid electrolyte interphase (SEI) has been proven to be a key enabler to most advanced battery chemistries, where the reactivity between the electrolyte and the anode operating beyond the electrolyte stability limits must be kinetically suppressed by such SEIs. The graphite anode used in state-of-the-art Li-ion batteries presents the most representative SEI example. Because of similar operation potentials between graphite and silicon (Si), a similar passivation mechanism has been thought to apply on the Si anode when using the same carbonate-based electrolytes. In this work, we found that the chemical formation process of a proto-SEI on Si is closely entangled with incessant SEI decomposition, detachment, and reparation, which lead to continuous lithium consumption. Using a special galvanostatic protocol designed to observe the SEI formation prior to Si lithiation, we were able to deconvolute the electrochemical formation of such dynamic SEI from the morphology and mechanical complexities of Si and showed that a pristine Si anode could not be fully passivated in carbonate-based electrolytes.
RESUMO
Silicon is a promising anode material for lithium-ion batteries because of its high capacity, but its widespread adoption has been hampered by a low cycle life arising from mechanical failure and the absence of a stable solid-electrolyte interphase (SEI). Understanding SEI formation and its impact on cycle life is made more complex by the oxidation of silicon materials in air or during synthesis, which leads to SiOx coatings of varying thicknesses that form the true surface of the electrode. In this paper, the lithiation of SiO2-coated Si is studied in a controlled manner using SiO2 coatings of different thicknesses grown on Si wafers via thermal oxidation. SiO2 thickness has a profound effect on lithiation: below 2 nm, SEI formation followed by uniform lithiation occurs at positive voltages versus Li/Li+. Si lithiation is reversible, and SiO2 lithiation is largely irreversible. Above 2 nm SiO2, voltammetric currents decrease exponentially with SiO2 thickness. For 2-3 nm SiO2, SEI formation above 0.1 V is suppressed, but a hold at low or negative voltages can initiate charge transfer whereupon SEI formation and uniform lithiation occur. Cycling of Si anodes with an SiO2 coating thinner than 3 nm occurs at high Coulombic efficiency (CE). If an SiO2 coating is thicker than 3-4 nm, the behavior is totally different: lithiation at positive voltages is strongly inhibited, and lithiation occurs at poor CE and is highly localized at pinholes which grow over time. As they grow, lithiation becomes more facile and the CE increases. Pinhole growth is proposed to occur via rapid transport of Li along the SiO2/Si interface radially outward from an existing pinhole, followed by the lithiation of SiO2 from the interface outward.
RESUMO
Transparent conductive adhesives (TCAs) can enable conductivity between two substrates, which is useful for a wide range of electronic devices. Here, we have developed a TCA composed of a polymer-particle blend with ethylene-vinyl acetate as the transparent adhesive and metal-coated flexible poly(methyl methacrylate) microspheres as the conductive particles that can provide conductivity and adhesion regardless of the surface texture. This TCA layer was designed to be nearly transparent, conductive in only the out-of-plane direction, and of practical adhesive strength to hold the substrates together. The series resistance was measured at 0.3 and 0.8 Ω cm2 for 8 and 0.2% particle coverage, respectively, while remaining over 92% was transparent in both cases. For applications in photovoltaic devices, such as mechanically stacked multijunction III-V/Si cells, a TCA with 1% particle coverage will have less than 0.5% power loss due to the resistance and less than 1% shading loss to the bottom cell.
RESUMO
One-dimensional nanostructures based on the Mo-S-I system have recently aroused a lot of interest as a viable alternative to the ubiquitous carbon nanotube due to their uniform structure and electronic properties for a given composition. Previous research on the Mo(6)S(3)I(6) and Mo(6)S(4.5)I(4.5) stoichiometries has also shown them to be soluble in common solvents like water, acetone or isopropyl alcohol, and to debundle on dilution. Here, the solubility, debundling and composition of Mo(6)S(2)I(8) nanowires are presented. They were found to be most soluble in dimethylformamide, which retained 47 wt% of a 0.08 gl(-1) nanowire (NW) material dispersion as thin NW bundles after one week. Dispersions of 0.8 gl(-1) and 5 gl(-1) even retained 54 wt% and 66 wt%, respectively. However the NW material was completely insoluble in water, and the surface energy of Mo(6)S(2)I(8) NWs was deduced as 67 mJ m(-2), higher than for other Mo-S-I NWs. UV-vis-NIR spectroscopy showed nanowire peaks familiar from Mo(6)S(3)I(6) and Mo(6)S(4.5)I(4.5) spectra around 1.8 and 2.8 eV, as well as unforeseen ultraviolet peaks at 3.5 and 4.4 eV. These chemical differences suggest an alternate, more strongly bonded structure to that seen for Mo(6)S(3)I(6) and Mo(6)S(4.5)I(4.5) NWs. Films deposited from a range of concentrations were investigated using atomic force microscopy (AFM) to determine bundle diameter distributions. The average diameter and the spread in diameters were found to decrease somewhat with decreasing concentration. However extrapolation gave a finite bundle size at infinite dilution, and an extension of the existing debundling model is proposed to take this into account. To confirm the nominal stoichiometry of Mo(6)S(2)I(8), which does not follow the generic Mo(6)S(x)I(9-x) formula of previous stoichiometries, EDX was carried out. The composition of nanowire bundles was found to be Mo(6)S(2.3)I(8.6), supporting the nominal composition.