An atomistically informed mesoscale model for growth and coarsening during discharge in lithium-oxygen batteries.

An atomistically informed mesoscale model is developed for the deposition of a discharge product in a Li-O2 battery. This mescocale model includes particle growth and coarsening as well as a simplified nucleation model. The model involves LiO2 formation through reaction of O2(-) and Li(+) in the electrolyte, which deposits on the cathode surface when the LiO2 concentration reaches supersaturation in the electrolyte. A reaction-diffusion (rate-equation) model is used to describe the processes occurring in the electrolyte and a phase-field model is used to capture microstructural evolution. This model predicts that coarsening, in which large particles grow and small ones disappear, has a substantial effect on the size distribution of the LiO2 particles during the discharge process. The size evolution during discharge is the result of the interplay between this coarsening process and particle growth. The growth through continued deposition of LiO2 has the effect of causing large particles to grow ever faster while delaying the dissolution of small particles. The predicted size evolution is consistent with experimental results for a previously reported cathode material based on activated carbon during discharge and when it is at rest, although kinetic factors need to be included. The approach described in this paper synergistically combines models on different length scales with experimental observations and should have applications in studying other related discharge processes, such as Li2O2 deposition, in Li-O2 batteries and nucleation and growth in Li-S batteries.

Miscibility Gap Closure, Interface Morphology, and Phase Microstructure of 3D Li(x)FePO4 Nanoparticles from Surface Wetting and Coherency Strain.

We study the mesoscopic effects which modify phase-segregation in LixFePO4 nanoparticles using a multiphysics phase-field model implement on a high performance cluster. We simulate 3D spherical particles of radii from 3 to 40 nm and examine the equilibrium microstructure and voltage profiles as they depend on size and overall lithiation. The model includes anisotropic, concentration-dependent elastic moduli, misfit strain, and facet dependent surface wetting within a Cahn-Hilliard formulation. We find that the miscibility gap vanishes for particles of radius ∼5 nm, and the solubility limits change with overall particle lithiation. Surface wetting stabilizes minority phases by aligning them with energetically beneficial facets. The equilibrium voltage profile is modified by these effects in magnitude, and the length and slope of the voltage plateau during two-phase coexistence.

Multicomponent phase-field model for extremely large partition coefficients.

We develop a multicomponent phase-field model specially formulated to robustly simulate concentration variations from molar to atomic magnitudes across an interface, i.e., partition coefficients in excess of 10±23 such as may be the case with species which are predominant in one phase and insoluble in the other. Substitutional interdiffusion on a normal lattice and concurrent interstitial diffusion are included. The composition in the interface follows the approach of Kim, Kim, and Suzuki [Phys. Rev. E 60, 7186 (1999)] and is compared to that of Wheeler, Boettinger, and McFadden [Phys. Rev. A 45, 7424 (1992)] in the context of large partitioning. The model successfully reproduces analytical solutions for binary diffusion couples and solute trapping for the demonstrated cases of extremely large partitioning.