Kinetic phase evolution of spinel cobalt oxide during lithiation

Li, Jing; He, Kai; Meng, Qingping; Li, Xin; Zhu, Yizhou; Hwang, Sooyeon; Sun, Ke; Gan, Hong; Zhu, Yimei; Mo, Yifei; Stach, Eric A.; Su, Dong

doi:10.1021/acsnano.6b04958

Kinetic phase evolution of spinel cobalt oxide during lithiation

Journal Article · Thu Sep 15 00:00:00 EDT 2016 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.6b04958· OSTI ID:1328370

Li, Jing ^[1]; He, Kai ^[2]; Meng, Qingping ^[2]; Li, Xin ^[3]; Zhu, Yizhou ^[4]; Hwang, Sooyeon ^[2]; Sun, Ke ^[2]; Gan, Hong ^[2]; Zhu, Yimei ^[2]; Mo, Yifei ^[4]; Stach, Eric A. ^[2]; Su, Dong ^[2]

Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., Stony Brook, NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Harvard Univ., Cambridge, MA (United States)
Univ. of Maryland, College Park, MD (United States)

Spinel cobalt oxide has been proposed to undergo a multiple-step reaction during the electrochemical lithiation process. Understanding the kinetics of the lithiation process in this compound is crucial to optimize its performance and cyclability. In this work, we have utilized a low-angle annular dark-field scanning transmission electron microscopy method to visualize the dynamic reaction process in real time and study the reaction kinetics at different rates. We show that the particles undergo a two-step reaction at the single-particle level, which includes an initial intercalation reaction followed by a conversion reaction. At low rates, the conversion reaction starts after the intercalation reaction has fully finished, consistent with the prediction of density functional theoretical calculations. At high rates, the intercalation reaction is overwhelmed by the subsequently nucleated conversion reaction, and the reaction speeds of both the intercalation and conversion reactions are increased. Phase-field simulations show the crucial role of surface diffusion rates of lithium ions in controlling this process. Furthermore, this work provides microscopic insights into the reaction dynamics in non-equilibrium conditions and highlights the effect of lithium diffusion rates on the overall reaction homogeneity as well as the performance.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials; Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2M)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0012673; SC0012704

OSTI ID:: 1328370

Report Number(s):: BNL--112671-2016-JA; KC0403020

Journal Information:: ACS Nano, Journal Name: ACS Nano; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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