Oxygen Reactions in a Non-Aqueous Li+ Electrolyte

Zhangquan Peng, Stefan A. Freunberger, Laurence J. Hardwick, Yuhui Chen, Vincent Giordani, Fanny Barde, Petr Novak, Duncan Graham, Jean-Marie Tarascon, Peter G. Bruce

Research output: Contribution to journalArticlepeer-review

424 Citations (Scopus)


Oxygen (O2) reduction is one of the most studied reactions in chemistry.1 Widely investigated in aqueous media, O2 reduction in non-aqueous solvents, such as CH3CN, has been studied for several decades.2–7 Today, O2 reduction in non-aqueous Li+ electrolytes is receiving considerable attention because it is the reaction on which operation of the Li–air (O2) battery depends.8–29 The Li–O2 battery is generating a great deal of interest because theoretically its high energy density could transform energy storage.8, 9 As a result, it is crucial to understand the O2 reaction mechanisms in non-aqueous Li+ electrolytes. Important progress has been made using electrochemical measurements including recently by Laoire et al.29 No less than five different mechanisms for O2 reduction in Li+ electrolytes have been proposed over the last 40 years based on electrochemical measurements alone.25–29 The value of using spectroelectrochemical methods is that they can identify directly the species involved in the reaction. Here we present in situ spectroscopic data that provide direct evidence that LiO2 is indeed an intermediate on O2 reduction, which then disproportionates to the final product Li2O2. Spectroscopic studies of Li2O2 oxidation demonstrate that LiO2 is not an intermediate on oxidation, that is, oxidation does not follow the reverse pathway to reduction.
Original languageEnglish
Pages (from-to)6351-6355
Number of pages5
JournalAgewandte Chemie-International Edition
Issue number28
Publication statusPublished - 4 Jul 2011


  • electrochemistry
  • lithium batteries
  • oxygen
  • reduction
  • surface enhanced Raman spectroscopy
  • ionic liquids
  • air batteries
  • raman-scattering
  • superoxide ion
  • electroreduction
  • dioxygen
  • TIC - Bionanotechnology


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