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December 17, 2015Science846 citationsOpen Access

Visualization of O-O peroxo-like dimers in high-capacity layered oxides for Li-ion batteries

EMEric McCallaAAArtem M. AbakumovMSMatthieu Saubanère

Key Points

  • Investigate and directly visualize the oxygen-oxygen bonding configurations and peroxo-like species associated with anionic redox reactions in high-capacity lithium-rich layered oxide cathodes.
  • Selected Li2IrO3 as a model layered oxide compound to study anionic redox behavior during initial delithiation.
  • Visualized atomic-scale structural configurations using transmission electron microscopy and neutron diffraction techniques.
  • Directly observed the formation and structural evolution of oxygen-oxygen (O-O) peroxo-like dimers within the delithiated layered oxide lattice.
  • Established the direct structural relationship between anionic redox activity and irreversible phase alterations occurring during first-cycle delithiation.

Abstract

Lithium-ion (Li-ion) batteries that rely on cationic redox reactions are the primary energy source for portable electronics. One pathway toward greater energy density is through the use of Li-rich layered oxides. The capacity of this class of materials (>270 milliampere hours per gram) has been shown to be nested in anionic redox reactions, which are thought to form peroxo-like species. However, the oxygen-oxygen (O-O) bonding pattern has not been observed in previous studies, nor has there been a satisfactory explanation for the irreversible changes that occur during first delithiation. By using Li2IrO3 as a model compound, we visualize the O-O dimers via transmission electron microscopy and neutron diffraction. Our findings establish the fundamental relation between the anionic redox process and the evolution of the O-O bonding in layered oxides.

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Cite This Study

McCalla et al. (2015) studied this question.

synapsesocial.com/papers/69daa1e88988aeabbe68705fhttps://doi.org/10.1126/science.aac8260
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