Surface Structural and Chemical Evolution of Layered LiNi < inf> 0.8 Co < inf> 0.15 Al < inf> 0.05 O < inf> 2 (NCA) under High Voltage and Elevated Temperature Conditions
Document Type
Article
Publication Date
12-11-2018
Abstract
© Copyright 2018 American Chemical Society. This paper reports new insights into structural and chemical evolution of surface phases of LiNi0.8Co0.15Al0.05O2 (NCA) held at constant high voltages (up to 4.75 V) as well as high temperatures (60 °C) by correlating crystal structure using high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) imaging with chemistry using electron energy loss spectroscopy (EELS). We also followed the Al distribution within individual NCA particles by X-ray energy dispersive spectroscopy (EDS). The progression of these phases as a function of distance from the edge shows simultaneous evolution of crystal structures and chemistry from rocksalt to layered, forming a complete solid solution. We have also observed an extended disordered phase with rocksalt (Fm3m) symmetry in which quantitative electron energy loss spectroscopy reveals it to be an oxygen deficient cation disordered phase with chemical characteristics, as determined by EELS, similar to spinel. The formation of these disordered phases with cation and oxygen vacancies has been driven by surface oxygen loss caused by reactions with the electrolyte followed by cation migration from the octahedral 3a M (M = Ni, Co, Al) layer to the octahedral 3b Li layer. These surface rocksalt phases are not fully dense as they contain Al and Li as well as a high concentration of cation and oxygen vacancies. After discharge, Li is detected within these phases indicative that Li transport has occurred through these rocksalt phases. At 60 °C and 4.75 V a very large impedance rise is observed leading to complete cell irreversibility which is caused by significant metal dissolution from the cathode and formation of surface porosity. In the near surface region of some particles, a phase transformation from R3m (O3) to P3m1 (O1) is also observed which has become thermodynamically stable from complete delithiation as well as from local Al surface depletion.
Publication Title
Chemistry of Materials
Recommended Citation
Mukherjee, P.,
Faenza, N.,
Pereira, N.,
Ciston, J.,
Piper, L.,
Amatucci, G.,
&
Cosandey, F.
(2018).
Surface Structural and Chemical Evolution of Layered LiNi < inf> 0.8 Co < inf> 0.15 Al < inf> 0.05 O < inf> 2 (NCA) under High Voltage and Elevated Temperature Conditions.
Chemistry of Materials,
30(23), 8431-8445.
http://doi.org/10.1021/acs.chemmater.7b05305
Retrieved from: https://digitalcommons.mtu.edu/michigantech-p/7798