Lithium-ion batteries continue to be a critical part of the search for enhanced energy storage solutions. Understanding the stability of interfaces (surfaces and grain boundaries) is one of the most crucial aspects of cathode design to improve the capacity and cyclability of batteries. Interfacial engineering through chemical modification offers the opportunity to create metastable states in the cathodes to inhibit common degradation mechanisms. Here, we demonstrate how atomistic simulations can effectively evaluate dopant interfacial segregation trends and be an effective predictive tool for cathode design despite the intrinsic approximations. We computationally studied two surfaces, {001} and {104}, and grain boundaries, Σ3 and Σ5, of LiCoO 2 to investigate the segregation potential and stabilization effect of dopants. Isovalent and aliovalent dopants (Mg 2+ , Ca 2+ , Sr 2+ , Sc 3+ , Y 3+ , Gd 3+ , La 3+ , Al 3+ , Ti 4+ , Sn 4+ , Zr 4+ , V 5+ ) were studied by replacing the Co 3+ sites in all four of the constructed interfaces. The segregation energies of the dopants increased with the ionic radius of the dopant. They exhibited a linear dependence on the ionic size for divalent, trivalent, and quadrivalent dopants for surfaces and grain boundaries. The magnitude of the segregation potential also depended on the surface chemistry and grain boundary structure, showing higher segregation energies for the Σ5 grain boundary compared with the lower energy Σ3 boundary and higher for the {104} surface compared to the {001}. Lanthanum-doped nanoparticles were synthesized and imaged with scanning transmission electron microscopy-electron energy loss spectroscopy (STEM-EELS) to validate the computational results, revealing the predicted lanthanum enrichment at grain boundaries and both the {001} and the {104} surfaces.

This work investigates the effects of doping on both the thermodynamics and kinetics of sintering in aluminum‐doped yttrium oxide nanoparticles (Al‐doped Y2O3), with the objective of delineating their interdependent effects at different stages of the process. Direct measurements of surface and grain boundary energies using differential scanning calorimetry showed that Al‐doping decreases both interfacial energies, leading to an increase in dihedral angle (from 152.7 ± 5.6° to 165.8 ± 5.5°) and, therefore, sintering stress. Densification and grain growth analyses showed that despite this increase in sintering stress, the onset of sintering is delayed for the Al‐doped samples, demonstrating that a large dihedral angle is a necessary but not sufficient condition for densification. The measurements of activation energies for densification and grain growth point out that Al suppresses grain boundary mobility by increasing the activation energy from 400 to 448 kJ/mol, hindering densification at the intermediate stages of sintering. At temperatures above 1150℃, grain growth is activated in the Al‐doped samples, which rapidly releases the accumulated sintering stress and exhibits a higher densification rate than in undoped Y2O3. This study demonstrates a complex interconnectivity between the thermodynamics and kinetics at different temperature ranges of sintering and reinforces the need for a comprehensive description for proper design of sintering aids.