Performance benchmarks for open source porous electrode theory models.

The electrochemical response characteristics of existing and emerging porous electrode theory (PET) models was benchmarked to establish a common basis to assess their physical reaches, limitations, and accuracy. Three open source PET models: dualfoil, MPET, and LIONSIMBA were compared to simulate the discharge of a LiMn2O4-graphite cell against experimental data. For C-rates below 2C, the simulated discharge voltage curves matched the experimental data within 4% deviation for dualfoil, MPET, and LIONSIMBA, while for C-rates above 3C, dualfoil and MPET show smaller deviations, within 5%, against experiments. The electrochemical profiles of all three codes exhibit significant qualitative differences, despite showing the same macroscopic voltage response, leading the user to different conclusions regarding the battery performance and possible degradation mechanisms of the analyzed system.

Toward Reservoir-on-a-Chip: Rapid Performance Evaluation of Enhanced Oil Recovery Surfactants for Carbonate Reservoirs Using a Calcite-Coated Micromodel.

Enhanced oil recovery (EOR) plays a significant role in improving oil production. Tertiary EOR, including surfactant flooding, can potentially mobilize residual oil after water flooding. Prior to the field deployment, the surfactant performance must be evaluated using site-specific crude oil at reservoir conditions. Core flood experiments are common practice to evaluate surfactants for oil displacement efficiency using core samples. Core flood experiments, however, are expensive and time-consuming and do not allow for pore scale observations of fluid-fluid interactions. This work introduces the framework to evaluate the performance of EOR surfactants via a Reservoir-on-a-Chip approach, which uses microfluidic devices to mimic the oil reservoir. A unique feature of this study is the use of chemically modified micromodels such that the pore surfaces are representative of carbonate reservoir rock. To represent calcium carbonate reservoir pores, the inner channels of glass microfluidic devices were coated with thin layers of calcium carbonate nanocrystals and the surface was modified to exhibit oil-wet conditions through a crude oil aging process. During surfactant screening, oil and water phases were imaged by fluorescence microscopy to reveal the micro to macro scale mechanisms controlling surfactant-assisted oil recovery. The role of the interfacial tension (IFT) and wettability in the microfluidic device was simulated using a phase-field model and compared to laboratory results. We demonstrated the effect of low IFT at the oil-water interface and wettability alteration on surfactant-enhanced oil displacement efficiency; thus providing a time-efficient and low-cost strategy for quantitative and qualitative assessment. In addition, this framework is an effective method for pre-screening EOR surfactants for use in carbonate reservoirs prior to further core and field scale testing.

Comprehensive comparison of pore-scale models for multiphase flow in porous media.

Multiphase flows in porous media are important in many natural and industrial processes. Pore-scale models for multiphase flows have seen rapid development in recent years and are becoming increasingly useful as predictive tools in both academic and industrial applications. However, quantitative comparisons between different pore-scale models, and between these models and experimental data, are lacking. Here, we perform an objective comparison of a variety of state-of-the-art pore-scale models, including lattice Boltzmann, stochastic rotation dynamics, volume-of-fluid, level-set, phase-field, and pore-network models. As the basis for this comparison, we use a dataset from recent microfluidic experiments with precisely controlled pore geometry and wettability conditions, which offers an unprecedented benchmarking opportunity. We compare the results of the 14 participating teams both qualitatively and quantitatively using several standard metrics, such as fractal dimension, finger width, and displacement efficiency. We find that no single method excels across all conditions and that thin films and corner flow present substantial modeling and computational challenges.

Origin and hysteresis of lithium compositional spatiodynamics within battery primary particles.

The kinetics and uniformity of ion insertion reactions at the solid-liquid interface govern the rate capability and lifetime, respectively, of electrochemical devices such as Li-ion batteries. Using an operando x-ray microscopy platform that maps the dynamics of the Li composition and insertion rate in Li(x)FePO4, we found that nanoscale spatial variations in rate and in composition control the lithiation pathway at the subparticle length scale. Specifically, spatial variations in the insertion rate constant lead to the formation of nonuniform domains, and the composition dependence of the rate constant amplifies nonuniformities during delithiation but suppresses them during lithiation, and moreover stabilizes the solid solution during lithiation. This coupling of lithium composition and surface reaction rates controls the kinetics and uniformity during electrochemical ion insertion.

The formation mechanism of eutectic microstructures in NiAl-Cr composites.

NiAl-based eutectic alloys, consisting of an ordered bcc matrix (B2) and disordered bcc fibers (A2), have been a subject of intensive efforts aimed at tailoring the properties of many of the currently used nickel-based superalloys. A thermodynamic phase field model was developed on a thermodynamic foundation and fully integrated with a thermo-kinetic database of the Ni-Al-Cr ternary system to elucidate the resulting peculiar eutectic microstructure. Invoking a variation of the liquid/solid interfacial thickness with temperature, we simulated the characteristic sunflower-like eutectic microstructures in the NiAl-Cr composites, consistent with experimental observations. The mechanism that governs the formation of the peculiar eutectic morphology was envisioned from the modeled evolutions associated with six sequential steps. Our calculations show that the conditional spinodal decomposition occurring in sequence could further trim and revise the microstructure of the eutectics by generating fine-domain structures, thereby providing an additional method to explore the novel NiAl-based eutectic composites with tunable properties at elevated temperatures.

Quantitative phase-field modeling of dendritic electrodeposition.

A thin-interface phase-field model of electrochemical interfaces is developed based on Marcus kinetics for concentrated solutions, and used to simulate dendrite growth during electrodeposition of metals. The model is derived in the grand electrochemical potential to permit the interface to be widened to reach experimental length and time scales, and electroneutrality is formulated to eliminate the Debye length. Quantitative agreement is achieved with zinc Faradaic reaction kinetics, fractal growth dimension, tip velocity, and radius of curvature. Reducing the exchange current density is found to suppress the growth of dendrites, and screening electrolytes by their exchange currents is suggested as a strategy for controlling dendrite growth in batteries.

Current-induced transition from particle-by-particle to concurrent intercalation in phase-separating battery electrodes.

Many battery electrodes contain ensembles of nanoparticles that phase-separate on (de)intercalation. In such electrodes, the fraction of actively intercalating particles directly impacts cycle life: a vanishing population concentrates the current in a small number of particles, leading to current hotspots. Reports of the active particle population in the phase-separating electrode lithium iron phosphate (LiFePO4; LFP) vary widely, ranging from near 0% (particle-by-particle) to 100% (concurrent intercalation). Using synchrotron-based X-ray microscopy, we probed the individual state-of-charge for over 3,000 LFP particles. We observed that the active population depends strongly on the cycling current, exhibiting particle-by-particle-like behaviour at low rates and increasingly concurrent behaviour at high rates, consistent with our phase-field porous electrode simulations. Contrary to intuition, the current density, or current per active internal surface area, is nearly invariant with the global electrode cycling rate. Rather, the electrode accommodates higher current by increasing the active particle population. This behaviour results from thermodynamic transformation barriers in LFP, and such a phenomenon probably extends to other phase-separating battery materials. We propose that modifying the transformation barrier and exchange current density can increase the active population and thus the current homogeneity. This could introduce new paradigms to enhance the cycle life of phase-separating battery electrodes.

Theory of coherent nucleation in phase-separating nanoparticles.

The basic physics of nucleation in solid single-crystal nanoparticles is revealed by a phase-field theory that includes surface energy, chemical reactions, and coherency strain. In contrast to binary fluids, which form arbitrary contact angles at surfaces, complete "wetting" by one phase is favored at binary solid surfaces. Nucleation occurs when surface wetting becomes unstable, as the chemical energy gain (scaling with area) overcomes the elastic energy penalty (scaling with volume). The nucleation barrier thus decreases with the area-to-volume ratio and vanishes below a critical size. Thus nanoparticles tend to transform in order of increasing size, leaving the smallest particles homogeneous (in the phase of lowest surface energy). The model is used to simulate phase separation in realistic nanoparticle geometries for LiXFePO4, a popular cathode material for Li-ion batteries, and collapses disparate experimental data for the nucleation barrier with no adjustable parameters. Beyond energy storage, the theory shows how to tailor the elastic and surface properties of a solid nanostructure to achieve desired phase behavior.

Coherency strain and the kinetics of phase separation in LiFePO4 nanoparticles.

A theoretical investigation of the effects of elastic coherency strain on the thermodynamics, kinetics, and morphology of intercalation in single LiFePO(4) nanoparticles yields new insights into this important battery material. Anisotropic elastic stiffness and misfit strains lead to the unexpected prediction that low-energy phase boundaries occur along {101} planes, while conflicting reports of phase boundary orientations are resolved by a partial loss of coherency in the [001] direction. Elastic relaxation near surfaces leads to the formation of a striped morphology with a characteristic length scale predicted by the model, yielding an estimate of the interfacial energy. The effects of coherency strain on solubility and galvanostatic discharge are studied with a reaction-limited phase-field model that quantitatively captures the influence of misfit strain, particle size, and temperature on solubility seen in experiments. Coherency strain strongly suppresses phase separation during discharge, which enhances rate capability and extends cycle life. The effects of elevated temperature and the feasibility of nucleation are considered in the context of multiparticle cathodes.

Suppression of phase separation in LiFePO4 nanoparticles during battery discharge.

Using a novel electrochemical phase-field model, we question the common belief that Li(X)FePO(4) nanoparticles always separate into Li-rich and Li-poor phases during battery discharge. For small currents, spinodal decomposition or nucleation leads to moving phase boundaries. Above a critical current density (in the Tafel regime), the spinodal disappears, and particles fill homogeneously, which may explain the superior rate capability and long cycle life of nano-LiFePO(4) cathodes.

Thermodynamic phase-field model for microstructure with multiple components and phases: the possibility of metastable phases.

A diffuse-interface model for microstructure with an arbitrary number of components and phases was developed from basic thermodynamic and kinetic principles and formalized within a variational framework. The model includes a composition gradient energy to capture solute trapping and is therefore suited for studying phenomena where the width of the interface plays an important role. Derivation of the inhomogeneous free energy functional from a Taylor expansion of homogeneous free energy reveals how the interfacial properties of each component and phase may be specified under a mass constraint. A diffusion potential for components was defined away from the dilute solution limit, and a multi-obstacle barrier function was used to constrain phase fractions. The model was used to simulate solidification via nucleation, premelting at phase boundaries and triple junctions, the intrinsic instability of small particles, and solutal melting resulting from differing diffusivities in solid and liquid. The shape of metastable free energy surfaces is found to play an important role in microstructure evolution and may explain why some systems premelt at phase boundaries and phase triple junctions, whereas others do not.