Tomographic reconstruction of oxygen orbitals in lithium-rich battery materials

The electrification of heavy-duty transport and aviation will require new strategies to increase the energy density of electrode materials(1,2). The use of anionic redox represents one possible approach to meeting this ambitious target. However, questions remain regarding the validity of the O2-/O- oxygen redox paradigm, and alternative explanations for the origin of the anionic capacity have been proposed(3), because the electronic orbitals associated with redox reactions cannot be measured by standard experiments. Here, using high-energy X-ray Compton measurements together with first-principles modelling, we show how the electronic orbital that lies at the heart of the reversible and stable anionic redox activity can be imaged and visualized, and its character and symmetry determined. We find that differential changes in the Compton profile with lithium-ion concentration are sensitive to the phase of the electronic wave function, and carry signatures of electrostatic and covalent bonding effects(4). Our study not only provides a picture of the workings of a lithium-rich battery at the atomic scale, but also suggests pathways to improving existing battery materials and designing new ones. High-energy X-ray Compton measurements and first-principles modelling reveal how the electronic orbital responsible for the reversible anionic redox activity can be imaged and visualized, and its character and symmetry determined.

Automated summary

High-energy X-ray Compton measurements and first-principles modelling reveal how the electronic orbital responsible for the reversible anionic redox activity can be imaged and visualized, and its character and symmetry determined. Differential changes in the Compton profile with lithium-ion concentration are sensitive to the phase of the electronic wave function, and carry signatures of electrostatic and covalent bonding effects.