Entering Voltage Hysteresis in Phase-Separating Materials: Revealing the Electrochemical Signature of the Intraparticle Phase-Separated State.

Hysteresis is a general phenomenon regularly observed in various materials. Usually, hysteretic behavior is an intrinsic property that cannot be circumvented in the nonequilibrium operation of the system. Herein, it is shown that, at least with regard to the hysteretic behavior of phase-separating battery materials, it is possible to enter (deeply) the hysteretic loop at finite battery currents. This newly observed electric response of the electrode, which is inherent to phase-separating materials, is related to its microscopic origin arising from a (significant) share of the active material residing in an intraparticle phase-separated state. This intriguing observation is further generalized by revealing that a phase-separating material can feature (significantly) different chemical potentials at the same bulk lithiation level and temperature when exposed to the same finite current and external voltage hysteresis. Therefore, the intraparticle phase-separated state significantly affects the DC and AC characteristics of the battery. The experimental evidence for entering the intraparticle phase-separated state is supported by thermodynamic reasoning and advanced modeling. The current findings will help advance the understanding, control, diagnostics, and monitoring of batteries composed of phase-separating materials while also providing pertinent motivation for the enhancement of battery design and performance.

Thermodynamically consistent derivation of chemical potential of a battery solid particle from the regular solution theory applied to LiFePO4.

The chemical potential of lithium in LixFePO4 active cathode nanoparticles and the surface free energy between LixFePO4 and electrolyte were determined with the novel thermodynamically consistent application of the regular solution theory. Innovative consideration of crystal anisotropy accounts for the consistent determination of the dependency of the chemical potential on the mechanistically derived enthalpy of mixing and the phase boundary gradient penalty. This enabled the analytic, thermodynamically consistent determination of the phase boundary thickness between LiFePO4 and FePO4, which is in good agreement with experimental observations. The obtained explicit functional dependency of the surface free energy on the lithium concentration enables adequate simulation of the initiation of the phase transition from FePO4 to LiFePO4 at the surface of active cathode particles. To validate the plausibility of the newly developed approaches, lithium intercalation into the LixFePO4 nanoparticles from electrolyte was modeled by solving the Cahn-Hilliard equation in a quasi-two-dimensional domain.

Effect of Rare Earth Elements on the Morphology of Eutectic Carbides in AISI D2 Tool Steels: Experimental and Modelling Approaches.

The morphology of the eutectic chromium carbides in the microstructure of as-cast AISI D2 tool steel was modified by adding small amounts of rare-earth elements (REEs) to the melt. As a result of these REE additions the eutectic carbide morphological type was changed from lamellar to globular. Similar phenomena have already been reported for various tool steels, but no complete theoretical explanation has been provided. Here, we propose a new model that is derived from first-principles thermodynamic calculations based on the phase-field modeling of the eutectic reaction. Using this new approach, where the decomposition of the phase-boundary surface-energy term is divided into the isotropic and anisotropic parts, we were able to account for the transition from a lamellar to a globular eutectic morphology in REE-modified AISI D2 tool steel.