Modeling Henry's law and phase separations of water-NaCl-organic mixtures with solvation and ion-pairing.

Empirical measurements of solution vapor pressure of ternary acetonitrile (MeCN) H2O-NaCl-MeCN mixtures were recorded, with NaCl concentrations ranging from zero to the saturation limit, and MeCN concentrations ranging from zero to an absolute mole fraction of 0.64. After accounting for speciation, the variability of the Henry's law coefficient at vapor-liquid equilibrium (VLE) of MeCN ternary mixtures decreased from 107% to 5.1%. Solute speciation was modeled using a mass action solution model that incorporates solute solvation and ion-pairing phenomena. Two empirically determined equilibrium constants corresponding to solute dissociation and ion pairing were utilized for each solute. When speciation effects were considered, the solid-liquid equilibrium of H2O-NaCl-MeCN mixtures appear to be governed by a simple saturation equilibrium constant that is consistent with the binary H2O-NaCl saturation coefficient. Further, our results indicate that the precipitation of NaCl in the MeCN ternary mixtures was not governed by changes in the dielectric constant. Our model indicates that the compositions of the salt-induced liquid-liquid equilibrium (LLE) boundary of the H2O-NaCl-MeCN mixture correspond to the binary plateau activity of MeCN, a range of concentrations over which the activity remains largely invariant in the binary water-MeCN system. Broader comparisons with other ternary miscible organic solvent (MOS) mixtures suggest that salt-induced liquid-liquid equilibrium exists if: (1) the solution displays a positive deviation from the ideal limits governed by Raoult's law; and (2) the minimum of the mixing free energy profile for the binary water-MOS system is organic-rich. This work is one of the first applications of speciation-based solution models to a ternary system, and the first that includes an organic solute.

Three-Dimensional Mapping of Resistivity and Microstructure of Composite Electrodes for Lithium-Ion Batteries.

Nanoparticle silicon-graphite composite electrodes are a viable way to advance the cycle life and energy density of lithium-ion batteries. However, characterization of composite electrode architectures is complicated by the heterogeneous mixture of electrode components and nanoscale diameter of particles, which falls beneath the lateral and depth resolution of most laboratory-based instruments. In this work, we report an original laboratory-based scanning probe microscopy approach to investigate composite electrode microstructures with nanometer-scale resolution via contrast in the electronic properties of electrode components. Applying this technique to silicon-based composite anodes demonstrates that graphite, SiOx nanoparticles, carbon black, and LiPAA binder are all readily distinguished by their intrinsic electronic properties, with measured electronic resistivity closely matching their known material properties. Resolution is demonstrated by identification of individual nanoparticles as small as ∼20 nm. This technique presents future utility in multiscale characterization to better understand particle dispersion, localized lithiation, and degradation processes in composite electrodes for lithium-ion batteries.

Solvent-driven fractional crystallization for atom-efficient separation of metal salts from permanent magnet leachates.

This work reports a dimethyl ether-driven fractional crystallization process for separating rare earth elements and transition metals. The process has been successfully applied in the treatment of rare earth element-bearing permanent magnet leachates as an atom-efficient, reagent-free separation method. Using ~5 bar pressure, the solvent was dissolved into the aqueous system to displace the contained metal salts as solid precipitates. Treatments at distinct temperatures ranging from 20-31 °C enable crystallization of either lanthanide-rich or transition metal-rich products, with single-stage solute recovery of up to 95.9% and a separation factor as high as 704. Separation factors increase with solution purity, suggesting feasibility for eco-friendly solution treatments in series and parallel to purify aqueous material streams. Staged treatments are demonstrated as capable of further improving the separation factor and purity of crystallized products. Upon completion of a crystallization, the solvent can be recovered with high efficiency at ambient pressure. This separation process involves low energy and reagent requirements and does not contribute to waste generation.

Mass action model of solution activity via speciation by solvation and ion pairing equilibria.

Solutes and their concentrations influence many natural and anthropogenic solution processes. Electrolyte and solution models are used to quantify and predict such behavior. Here we present a mechanistic solution model based on mass action equilibria. Solvation and ion pairing are used to model speciated solute and solvent concentrations such that they correlate to a solution's vapor pressure (solvent activity) according to Raoult's law from dilute conditions to saturation. This model introduces a hydration equilibrium constant (Kha) that is used with either an ion dissociation constant (Kid) or a hydration modifier (m) with an experimentally determined ion dissociation constant, as adjustable parameters to fit vapor-liquid equilibrium data. The modeled solvation equilibria are accompanied by molecular dynamics (MD) studies that support a decline in the observed degree of solvation with increased concentration. MD calculations indicate this finding is a combination of a solvent that solvates multiple solutes, and changes in a solute's solvation sphere, with the dominant factor changing with concentration. This speciation-based solution model is lateral to established electrostatics-based electrolyte theories. With its basis in mass action, the model can directly relate experimental data to the modeled solute and solvent speciated concentrations and structures.

Surface SiO2 Thickness Controls Uniform-to-Localized Transition in Lithiation of Silicon Anodes for Lithium-Ion Batteries.

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.

Effect of Water Concentration in LiPF6-Based Electrolytes on the Formation, Evolution, and Properties of the Solid Electrolyte Interphase on Si Anodes.

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 ∼1.0 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.

Intrinsic Properties of Individual Inorganic Silicon-Electrolyte Interphase Constituents.

Because of the complexity, high reactivity, and continuous evolution of the silicon-electrolyte interphase (SiEI), "individual" constituents of the SiEI were investigated to understand their physical, electrochemical, and mechanical properties. For the analysis of these intrinsic properties, known SiEI components (i.e., SiO2, Li2Si2O5, Li2SiO3, Li3SiOx, Li2O, and LiF) were selected and prepared as amorphous thin films. The chemical composition, purity, morphology, roughness, and thickness of prepared samples were characterized using a variety of analytical techniques. On the basis of subsequent analysis, LiF shows the lowest ionic conductivity and relatively weak, brittle mechanical properties, while lithium silicates demonstrate higher ionic conductivities and greater mechanical hardness. This research establishes a framework for identifying components critical for stabilization of the SiEI, thus enabling rational design of new electrolyte additives and functional binders for the development of next-generation advanced Li-ion batteries utilizing Si anodes.

Mechanical Properties and Chemical Reactivity of Li xSiO y Thin Films.

Silicon (Si) is a commonly studied candidate material for next-generation anodes in Li-ion batteries. A native oxide SiO2 on Si is often inevitable. However, it is not clear if this layer has a positive or negative effect on the battery performance. This understanding is complicated by the lack of knowledge about the physical properties of the SiO2 lithiation products and by the convolution of chemical and electrochemical effects during the anode lithiation process. In this study, Li xSiO y thin films as model materials for lithiated SiO2 were deposited by magnetron sputtering at ambient temperature, with the goal of (1) decoupling chemical reactivity from electrochemical reactivity and (2) evaluating the physical and electrochemical properties of Li xSiO y. X-ray photoemission spectroscopy analysis of the deposited thin films demonstrate that a composition close to previous experimental reports of lithiated native SiO2 can be achieved through sputtering. Our density functional theory calculations also confirm that the possible phases formed by lithiating SiO2 are very close to the measured film compositions. Scanning probe microscopy measurements show that the mechanical properties of the film are strongly dependent on lithium concentration, with a ductile behavior at a higher Li content and a brittle behavior at a lower Li content. The chemical reactivity of the thin films was investigated by measuring the AC impedance evolution, suggesting that Li xSiO y continuously reacts with the electrolyte, in part because of the high electronic conductivity of the film determined from solid-state impedance measurements. The electrochemical cycling data of the sputter-deposited Li xSiO y/Si films also suggest that Li xSiO y is not beneficial in stabilizing the Si anode surface during battery operation, despite its favorable mechanical properties.

Mechanical Properties and Chemical Reactivity of LixSiOy Thin Films.

Silicon (Si) is a commonly studied candidate material for next-generation anodes in Li-ion batteries. A native oxide SiO2 on Si is often inevitable. However, it is not clear if this layer has positive or negative effect on the battery performance. This understanding is complicated by the lack of knowledge about the physical properties, and by convolution of chemical and electrochemical effects during the anode lithiation process. In this study, LixSiOy thin films as model materials for lithiated SiO2 were deposited by magnetron sputtering at ambient temperature, with the goal of 1) decoupling chemical reactivity from electrochemical reactivity, and 2) evaluating the physical and electrochemical properties of LixSiOy. XPS analysis of the deposited thin films demonstrate that a composition close to previous experimental reports of lithiated native SiO2, can be achieved through sputtering. Our density functional theory calculations also confirm that possible phases formed by lithiating SiO2 are very close to the measured film compositions. Scanning probe microscopy measurements show the mechanical properties of the film are strongly dependent on lithium concentration, with ductile behavior and higher Li content and brittle behavior at lower Li content. Chemical reactivity of the thin films was investigated by measuring AC impedance evolution, suggesting that LixSiOy continuously reacts with electrolyte, in part due to high electronic conductivity of the film determined from solid state impedance measurements. Electrochemical cycling data of sputter deposited LixSiOy/Si films also suggest that LixSiOy is not beneficial in stabilizing the Si anode surface during battery operation, despite its favorable mechanical properties.