In-situ formation of spinel protective layer through extremely low K-doping for enhanced performance of Ni-rich layered cathodes
Journal
Journal of Power Sources
Journal Volume
623
Start Page
235446
ISSN
0378-7753
Date Issued
2024-12-15
Author(s)
Wei-Hsiang Chen
Yu-Ting Weng
Yu-Cheng Lu
Hsi Chen
Po-Ya Chang
Hwo-Shuenn Sheu
Senthil-Kumar Parthasarathi
DOI
10.1016/j.jpowsour.2024.235446
Abstract
Herein, we demonstrate a novel and feasible strategy to stabilize the LiNi0.83Co0.12Mn0.05O2 (NCM) structure via the in-situ formation of a superficial spinel layer with potassium (K) doping. While K+ doped NCM is not new, the formation of the protective spinel layer gives surprising results with even a trace amount of doping, which is unique and novel, and nowhere reported. The structural transformation from layered to spinel on the surface region of NCM is achieved with a K-doping level of 0.05 mol% (NCM-0.05K) and the formed spinel layer acted as a protective pillar for stabilizing the host structure, leading to substantially improved electrochemical performance. The X-ray photoelectron spectra demonstrate a large increase in nickel (Ni2+) distribution after cycling for pristine but almost no change for the NCM-0.05K, suggesting a stable preformed spinel layer. The above results reveal that the K+ doping can strongly reduce the Ni4+ to stable Ni2+ under the spinel phase formation and improves cell performances in terms of specific capacity, capacity retention, rate capability, and Li+ diffusivity. The internal micro-cracking of host NCM is also effectively suppressed by the low amount of K doping. Excessive K-doping, in contrast, leads to a reduction in (de)lithiation rate and greater polarization.
Subjects
Cycling stability
K-doping
Lithium-ion transport
Ni-rich cathode
rate performance
Surface stabilization
Publisher
Elsevier BV
Type
journal article