Atomistic Simulation Informs Interface Engineering of Nanoscale LiCoO2

Spencer Dahl; Toshihiro Aoki; Amitava Banerjee; Blas Pedro Uberuaga; Ricardo H R Castro

doi:10.1021/acs.chemmater.2c01246

Atomistic Simulation Informs Interface Engineering of Nanoscale LiCoO₂

Chem Mater. 2022 Sep 13;34(17):7788-7798. doi: 10.1021/acs.chemmater.2c01246. Epub 2022 Aug 19.

Authors

Spencer Dahl¹, Toshihiro Aoki², Amitava Banerjee³, Blas Pedro Uberuaga⁴, Ricardo H R Castro¹

Affiliations

¹ Department of Materials Science and Engineering, University of California, Davis, California 95616, United States.
² Irvine Materials Research Institute (IMRI), University of California, Irvine, California 92697, United States.
³ Department of Metallurgical and Materials Engineering, Indian Institute of Technology, Jodhpur, Rajasthan 342030, India.
⁴ Materials Science and Technology Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States.

Abstract

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 LiCoO₂ to investigate the segregation potential and stabilization effect of dopants. Isovalent and aliovalent dopants (Mg²⁺, Ca²⁺, Sr²⁺, Sc³⁺, Y³⁺, Gd³⁺, La³⁺, Al³⁺, Ti⁴⁺, Sn⁴⁺, Zr⁴⁺, V⁵⁺) were studied by replacing the Co³⁺ 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.