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Title: Lithium superoxide encapsulated in a benzoquinone anion matrix
Lithium peroxide is the crucial storage material in lithium–air batteries. Understanding the redox properties of this salt is paramount toward improving the performance of this class of batteries. Lithium peroxide, upon exposure to p –benzoquinone ( p –C 6 H 4 O 2 ) vapor, develops a deep blue color. This blue powder can be formally described as [Li 2 O 2 ] 0.3   · [LiO 2 ] 0.7   · {Li[ p –C 6 H 4 O 2 ]} 0.7 , though spectroscopic characterization indicates a more nuanced structural speciation. Infrared, Raman, electron paramagnetic resonance, diffuse-reflectance ultraviolet-visible and X-ray absorption spectroscopy reveal that the lithium salt of the benzoquinone radical anion forms on the surface of the lithium peroxide, indicating the occurrence of electron and lithium ion transfer in the solid state. As a result, obligate lithium superoxide is formed and encapsulated in a shell of Li[ p –C 6 H 4 O 2 ] with a core of Li 2 O 2 . Lithium superoxide has been proposed as a critical intermediate in the charge/discharge cycle of Li–air batteries, but has yet to be isolated, owing to instability. The results reported herein provide a snapshot of lithium peroxide/superoxide chemistry in the solid state with redox mediation.  more » « less
Award ID(s):
1954515
NSF-PAR ID:
10320709
Author(s) / Creator(s):
; ; ; ; ; ;
Date Published:
Journal Name:
Proceedings of the National Academy of Sciences
Volume:
118
Issue:
51
ISSN:
0027-8424
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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    Acknowledgment

    This work was partially supported by the U.S. National Science Foundation (NSF) Award No. ECCS-1931088. S.L. and H.W.S. acknowledge the support from the Improvement of Measurement Standards and Technology for Mechanical Metrology (Grant No. 22011044) by KRISS.

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