Diagnostics of lithium-ion intercalation rate-determining step: Distinguishing between slow desolvation and slow charge transfer

Sergey Yu Vassiliev, Vyacheslav V. Sentyurin, Eduard E. Levin, Victoria A. Nikitina

Research output: Contribution to journalArticlepeer-review

22 Citations (Scopus)

Abstract

The elucidation of the reaction rate-determining step nature in intercalation processes is essential for the development of approaches for the precise control of rate-limiting factors. In this work, we explore the kinetic patterns of lithium-ion intercalation into two model cathode materials (LiCoO 2 and LiMn 2 O 4 ) and develop criteria for distinguishing between Butler-Volmer slow charge transfer and slow chemical steps. A numerical model for the rate-limiting ion desolvation step is developed and the predictions of the model are compared with the experimental voltammetric and electrochemical impedance spectroscopy data. We show that slow desolvation step results in essential changes in the shape of both cyclic voltammetry and impedance responses with the kinetic resistance vs. potential dependencies being highly informative for the reaction rate control diagnostics. The consideration of the intercalation kinetics in four solvents (water, propylene carbonate, acetonitrile and dimethyl sulfoxide) allows concluding on the influence of the resistivity of surface layer/electrode material interface on the reaction slow step nature.

Original languageEnglish
Pages (from-to)316-326
Number of pages11
JournalElectrochimica Acta
Volume302
DOIs
Publication statusPublished - 10 Apr 2019

Keywords

  • Electrochemical impedance spectroscopy
  • Intercalation kinetics
  • Ion desolvation
  • Lithium-ion battery
  • Rate-determining step

Fingerprint

Dive into the research topics of 'Diagnostics of lithium-ion intercalation rate-determining step: Distinguishing between slow desolvation and slow charge transfer'. Together they form a unique fingerprint.

Cite this