NDLI: Short-range Li diffusion vs. long-range ionic conduction in nanocrystalline lithium peroxide Li2O2—the discharge product in lithium-air batteries

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Short-range Li diffusion vs. long-range ionic conduction in nanocrystalline lithium peroxide Li₂O₂—the discharge product in lithium-air batteries

Content Provider	Royal Society of Chemistry (RSC)
Author	Freunberger, S. A. Dunst, A. Epp, V. Hanzu, I. Wilkening, M.
Copyright Year	2014
Abstract	Understanding charge carrier transport in Li2O2, the storage material in the non-aqueous Li-O2 battery, is key to the development of this high-energy battery. Here, we studied ionic transport properties and Li self-diffusion in nanocrystalline Li2O2 by conductivity and temperature variable 7Li NMR spectroscopy. Nanostructured Li2O2, characterized by a mean crystallite size of less than 50 nm as estimated from X-ray diffraction peak broadening, was prepared by high-energy ball milling of microcrystalline lithium peroxide with μm sized crystallites. At room temperature the overall conductivity σ of the microcrystalline reference sample turned out to be very low (3.4 × 10−13 S cm−1) which is in agreement with results from temperature-variable 7Li NMR line shape measurements. Ball-milling, however, leads to an increase of σ by approximately two orders of magnitude (1.1 × 10−10 S cm−1); correspondingly, the activation energy decreases from 0.89 eV to 0.82 eV. The electronic contribution σeon, however, is in the order of 9 × 10−12 S cm−1 which makes less than 10% of the total value. Interestingly, 7Li NMR lines of nano-Li2O2 undergo pronounced heterogeneous motional narrowing which manifests in a two-component line shape emerging with increasing temperatures. Most likely, the enhancement in σ can be traced back to the generation of a spin reservoir with highly mobile Li ions; these are expected to reside in the nearest neighbourhood of defects generated or near the structurally disordered and defect-rich interfacial regions formed during mechanical treatment.
Starting Page	2739
Ending Page	2752
Page Count	14
File Format	HTM / HTML PDF
ISSN	17545692
Volume Number	7
Issue Number	8
Journal	Energy & Environmental Science
DOI	10.1039/c4ee00496e
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Subscribed
Subject Keyword	Li Charge carrier Self-diffusion Nuclear magnetic resonance spectroscopy Crystallite X-ray crystallography Peroxide Micrometre Nuclear magnetic resonance Activation energy Electronvolt Motional narrowing Petroleum reservoir
Content Type	Text
Resource Type	Article
Subject	Environmental Chemistry Pollution Renewable Energy, Sustainability and the Environment Nuclear Energy and Engineering

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