Effect of Ambient Storage on the Degradation of Ni-Rich Positive Electrode Materials (NMC811) for Li-Ion Batteries

TLDR

Layered LiNi₀.₈Mn₀.₁Co₀.₁O₂ (NMC811) is a high‑energy cathode material for next‑generation Li‑ion batteries, but its higher surface reactivity compared to NMC111 leads to a shorter lifetime. The study aimed to compare surface contamination formation on NMC811 and NMC111 during ambient storage using electrochemical cycling, Raman spectroscopy, and X‑ray photoelectron spectroscopy. Surface carbonate species were quantified by GC detection of CO₂ released when the particles were dispersed in hydrochloric acid, and electrochemical cycling, Raman spectroscopy, and X‑ray photoelectron spectroscopy were used to characterize surface contamination. After one year of ambient storage, NMC811 develops a ~10 nm surface layer of nickel carbonate (with minor hydroxide and water) that causes a pronounced delithiation voltage peak during first charge and markedly degrades the cycling stability of NMC811‑graphite cells, whereas NMC111 shows no significant surface changes.

Abstract

Layered LiNi0.8Mn0.1Co0.1O2 (NMC811) is one of the high-energy positive electrode (cathode) materials for next generation Li-ion batteries. However, compared to the structurally similar LiNi1/3Mn1/3Co1/3O2 (NMC111), it can suffer from a shorter lifetime due to its higher surface reactivity. This work studied and compared the formation of surface contaminations on NMC811 and NMC111 when stored under ambient conditions using electrochemical cycling, Raman spectroscopy, and X-ray photoelectron spectroscopy. NMC811 was found to develop a surface layer of up to ∼10 nm thickness that was mostly composed of nickel carbonate species mixed with minor quantities of hydroxide and water after ambient storage for 1 year, while no significant changes were observed on the NMC111 surface. The amount of carbonate species was quantified by gas chromatographic (GC) detection of carbon dioxide generated when the NMC particles were dispersed in hydrochloric acid. Surface impurity species formed on NMC811 upon ambient storage not only lead to a significant delithiation voltage peak in the first charge, but also markedly reduce the cycling stability of NMC811-graphite cells due to significantly growing polarization of the NMC811 electrode.