Ni-rich layered cathode materials are important candidates for lithium-ion batteries used for high energy density applications, such as electric vehicles. However, these materials are suffering severe capacity fade caused by surface reconstruction, unstable cathode-electrolyte interface (CEI) formation and micro crack formation during cycling, especially when a high cut off charge voltage is applied (such as 4.6 and 4.8V). To understand the origin of this capacity fade, state-of-the-art diagnostic tools are applied to understand their structure, chemical and morphological properties of LiNi_0.94Co_0.06O₂ (NC) and LiNi_0.92Co_0.06Al_0.02O₂ (NCA) cathode materials during cycling. Electrochemical measurement results show that the NCA cathode delivered higher capacity and stable cyclic performance even cycled at a high cut of voltage of 4.8V. In situ X-ray absorption spectroscopy (XAS) results of NC and NCA electrodes measured during the first and 51^st charge/discharge cycling between the voltage range of 2.8-4.4V showed that both Ni and Co contribute to the capacity by going through the Ni³⁺/Ni⁴⁺ and Co³⁺/Co⁴⁺ redox couples. The Ni-K edge XAS spectra of NC cathode charged to 4.8V showed slightly reduction of Ni⁴⁺ during the high voltage charging. While, XAS spectra of NCA cathode did not showed reduction of Ni⁴⁺ when the cell charged to the higher voltage. More interestingly, C, F, O, Ni and Co soft XAS spectroscopy of NC and NCA electrodes at the different state of charge provided more comprehensive insight into surface and bulk chemical properties. The results showed that much thicker CEI layer formed on the NC surface compared with the NCA cathode, indicated that Al-doping effectively reduced the side reaction of cathode materials with the electrolyte. We have also compared the morphological and chemical evolution of NC and NCA secondary particles using full-filed in-situ transmission X-ray microscopy (TXM) during the initial cycle. Results will be presented at the meeting.

Acknowledgement

This project was supported by the U.S. Department of Energy, the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies through Advanced Battery Material Research (BMR) program (Battery500 consortium) under Contract No. DESC0012704.