Microstructural Degradation of Ni‐Rich Li[NixCoyMn1−x−y]O2 Cathodes During Accelerated Calendar Aging. Issue 45 (14th September 2018)

• Record Type: Journal Article
• Authors: Ryu, Hoon‐Hee; Park, Geon‐Tae; Yoon, Chong S.; Sun, Yang‐Kook
• Is Part Of: Small. Volume 14:Issue 45(2018)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2018-09-14
• Subjects: calendar aging -- microcracks -- microstructural degradation -- Ni‐rich layered Li[NixCoyMn1−x−y]O2 -- TEM analysis; Nanotechnology -- Periodicals; Nanoparticles -- Periodicals; Microtechnology -- Periodicals; 620.5
• DOI: 10.1002/smll.201803179
• Languages: English
• ISSNs: 1613-6810

Abstract

Abstract: Because electric vehicles (EVs) are used intermittently with long resting periods in the fully charged state before driving, calendar aging behavior is an important criterion for the application of Li‐ion batteries used in EVs. In this work, Ni‐rich Li[Ni x Co y Mn1 −x−y ]O2 ( x = 0.8 and 0.9) cathode materials with high energy densities, but low cycling stabilities are investigated to characterize their microstructural degradation during accelerated calendar aging. Although the particles seem to maintain their crystal structures and morphologies, the microcracks which develop during calendar aging remain even in the fully discharged state. An NiO‐like phase rock‐salt structure of tens of nanometers in thickness accumulates on the surfaces of the primary particles through parasitic reactions with the electrolyte. In addition, the passive layer of this rock‐salt structure near the microcracks is gradually exfoliated from the primary particles, exposing fresh surfaces containing Ni 4+ to the electrolyte. Interestingly, the interior primary particles near the microcracks have deteriorated more severely than the outer particles. The microstructural degradation is worsened with increasing Ni contents in the cathode materials, directly affecting electrochemical performances such as the reversible capacities and voltage profiles. Abstract : Microstructural degradation of Ni‐rich Li[Nix Coy Mn1–x–y ]O2 cathode materials during calendar aging is reported. Because of parasitic reactions, microcracks develop and remain across the entire secondary particle, even after discharging. An NiO‐like phase rock‐salt structure accumulates and exfoliates from the main particles, continuously exposing fresh surfaces. This phenomenon reflects in the electrochemical performance including the discharge capacity and the voltage profile.