NMR monitoring of electrode/electrolyte interphase in the case of air-exposed and carbon coated LiFePO4

Marine Cuisinier, N. Dupré, P. Moreau, D. Guyomard

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

Degradation of the electrochemical performance of LiFePO4 upon air exposure, assigned to a corrosion-type aging mechanism, implies the incorporation of hydroxyl groups and the formation of an amorphous tavorite-like phase at the surface. Using a carbon coating provides an efficient protection from this detrimental process but also modifies the surface in contact with the electrolyte. The formation and evolution of electrode/electrolyte interphases forming on both air-aged and carbon coated LiFePO4 are discussed based on combined quantitative 7Li, 19F MAS NMR, EIS and EELS measurements. Concerning the air-aged LiFePO4, the electrode/electrolyte interactions are dominated by the dissolution of the active material and an exacerbated reaction of incorporated hydroxyl groups with the electrolyte salt, resulting in a LiF rich interphase. This dissolution of the outer part of active material particles is accompanied by the departure of the previously formed interphase and a new interphase is then formed on a newly exposed surface. The resistive LiF rich interphase passivates the active material particles during cycling, forming a resistive film, hindering both Li ion transfer and material corrosion. Cellulose acetate based carbon coating prevents air-aging but yields to an accumulation of organic lithiated species, allowing Li transfer and maintaining good electrochemical performance.

Original languageEnglish
Pages (from-to)682-690
Number of pages9
JournalJournal of Power Sources
Volume243
DOIs
Publication statusPublished - 2013
Externally publishedYes

Fingerprint

Electrolytes
Carbon
Nuclear magnetic resonance
electrolytes
nuclear magnetic resonance
Electrodes
electrodes
Monitoring
carbon
air
Air
Hydroxyl Radical
corrosion
dissolving
Dissolution
Aging of materials
Corrosion
coatings
Coatings
Electron energy loss spectroscopy

Keywords

  • Interface
  • Lithium batteries
  • MAS NMR
  • Positive electrode

ASJC Scopus subject areas

  • Electrical and Electronic Engineering
  • Energy Engineering and Power Technology
  • Renewable Energy, Sustainability and the Environment
  • Physical and Theoretical Chemistry

Cite this

NMR monitoring of electrode/electrolyte interphase in the case of air-exposed and carbon coated LiFePO4. / Cuisinier, Marine; Dupré, N.; Moreau, P.; Guyomard, D.

In: Journal of Power Sources, Vol. 243, 2013, p. 682-690.

Research output: Contribution to journalArticle

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