Defects and nanostrain gradients control phase transition mechanisms in single crystal high-voltage lithium spinel

Isaac Martens, Nikita Vostrov, Marta Mirolo, Steven J. Leake, Edoardo Zatterin, Xiaobo Zhu, Lianzhou Wang, Jakub Drnec, Marie-Ingrid Richard () and Tobias U. Schulli ()
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Isaac Martens: ESRF - The European Synchrotron
Nikita Vostrov: ESRF - The European Synchrotron
Marta Mirolo: ESRF - The European Synchrotron
Steven J. Leake: ESRF - The European Synchrotron
Edoardo Zatterin: ESRF - The European Synchrotron
Xiaobo Zhu: Changsha University of Science and Technology
Lianzhou Wang: University of Queensland
Jakub Drnec: ESRF - The European Synchrotron
Marie-Ingrid Richard: ESRF - The European Synchrotron
Tobias U. Schulli: ESRF - The European Synchrotron

Nature Communications, 2023, vol. 14, issue 1, 1-10

Abstract: Abstract Lithiation dynamics and phase transition mechanisms in most battery cathode materials remain poorly understood, because of the challenge in differentiating inter- and intra-particle heterogeneity. In this work, the structural evolution inside Li1−xMn1.5Ni0.5O4 single crystals during electrochemical delithiation is directly resolved with operando X-ray nanodiffraction microscopy. Metastable domains of solid-solution intermediates do not appear associated with the reaction front between the lithiated and delithiated phases, as predicted by current phase transition theory. Instead, unusually persistent strain gradients inside the single crystals suggest that the shape and size of solid solution domains are instead templated by lattice defects, which guide the entire delithiation process. Morphology, strain distributions, and tilt boundaries reveal that the (Ni2+/Ni3+) and (Ni3+/Ni4+) phase transitions proceed through different mechanisms, offering solutions for reducing structural degradation in high voltage spinel active materials towards commercially useful durability. Dynamic lattice domain reorientation during cycling are found to be the cause for formation of permanent tilt boundaries with their angular deviation increasing during continuous cycling.

Date: 2023
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DOI: 10.1038/s41467-023-42285-4

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