Limitations of Ultrathin Al₂O₃ Coatings on LNMO Cathodes.

ABSTRACT: This study demonstrates the application of Al₂O₃ coatings for the high-voltage cathode material LiNi_0.5-x Mn_1.5+x O_4-δ (LNMO) by atomic layer deposition. The ultrathin and uniform coatings (0.6-1.7 nm) were deposited on LNMO particles and characterized by scanning transmission electron microscopy, inductively coupled plasma mass spectrometry, and X-ray photoelectron spectroscopy. Galvanostatic charge discharge cycling in half cells revealed, in contrast to many published studies, that even coatings of a thickness of 1 nm were detrimental to the cycling performance of LNMO. The complete coverage of the LNMO particles by the Al₂O₃ coating can form a Li-ion diffusion barrier, which leads to high overpotentials and reduced reversible capacity. Several reports on Al₂O₃-coated LNMO using alternative coating methods, which would lead to a less homogeneous coating, revealed the superior electrochemical properties of the Al₂O₃-coated LNMO, suggesting that complete coverage of the particles might in fact be a disadvantage. We show that transition metal ion dissolution during prolonged cycling at 50 °C is not hindered by the coating, resulting in Ni and Mn deposits on the Li counter electrode. The Al₂O₃-coated LNMO particles showed severe signs of pitting dissolution, which may be attributed to HF attack caused by side reactions between the electrolyte and the Al₂O₃ coating, which can lead to additional HF formation. The pitting dissolution was most severe for the thickest coating (1.7 nm). The uniform coating coverage may lead to non-uniform conduction paths for Li, where the active sites are more susceptible to HF attack. Few benefits of applications of very thin, uniform, and amorphous Al₂O₃ coatings could thus be verified, and the coating is not offering long-term protection from HF attack.

SUBMITTER: Ostli ER 

PROVIDER: S-EPMC8603187 | biostudies-literature |

REPOSITORIES: biostudies-literature