Biomaterial Database

Electrolyte-Induced Surface Transformation and Transition-Metal Dissolution of Fully Delithiated LiNi0.8Co0.15Al0.05O2. 2017

Nicholas V Faenza, and Zachary W Lebens-Higgins, and Pinaki Mukherjee, and Shawn Sallis, and Nathalie Pereira, and Fadwa Badway, and Anna Halajko, and Gerbrand Ceder, and Frederic Cosandey, and Louis F J Piper, and Glenn G Amatucci

Energy Storage Research Group, Department of Materials Science and Engineering, Rutgers University , North Brunswick, New Jersey 08902, United States.

Enabling practical utilization of layered R3̅m positive electrodes near full delithiation requires an enhanced understanding of the complex electrode-electrolyte interactions that often induce failure. Using Li[Ni0.8Co0.15Al0.05]O2 (NCA) as a model layered compound, the chemical and structural stability in a strenuous thermal and electrochemical environment was explored. Operando microcalorimetry and electrochemical impedance spectroscopy identified a fingerprint for a structural decomposition and transition-metal dissolution reaction that occurs on the positive electrode at full delithiation. Surface-sensitive characterization techniques, including X-ray absorption spectroscopy and high-resolution transmission electron microscopy, measured a structural and morphological transformation of the surface and subsurface regions of NCA. Despite the bulk structural integrity being maintained, NCA surface degradation at a high state of charge induces excessive transition-metal dissolution and significant positive electrode impedance development, resulting in a rapid decrease in electrochemical performance. Additionally, the impact of electrolyte salt, positive electrode surface area, and surface Li2CO3 content on the magnitude and character of the dissolution reaction was studied.