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Investigate the electronic structure and dynamic crystallographic transformations of a Li-rich Mn–Ni layered oxide cathode material during electrochemical battery cycling.

January 1, 2012Journal of Materials Chemistry

In situ investigations of a Li-rich Mn–Ni layered oxide for Li-ion batteries

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Authors

LSLoïc SimoninUniversité Claude Bernard Lyon 1 JCJ. ColinCommissariat à l'Énergie Atomique et aux Énergies Alternatives VRV. RanieriÉcole Nationale Supérieure de Chimie de Montpellier

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Implication

Experimental investigation reveals irreversible phase transformation during initial charging of lithium-rich layered oxide cathodes, indicating permanent structural reorganization during cycling.

Key Points

Investigate the electronic structure and dynamic crystallographic transformations of a Li-rich Mn–Ni layered oxide cathode material during electrochemical battery cycling.
Synthesized a lithium-rich layered cathode material with the nominal composition Li[Li0.2Mn0.61Ni0.18Mg0.01]O2.
Tracked structural phase changes and transition metal electronic states using in situ X-ray diffraction (XRD), extended X-ray absorption fine structure (EXAFS), and X-ray absorption near-edge structure (XANES).
Characterized initial transition metal oxidation configurations using SQUID magnetometry.
Pristine manganese exhibits an average oxidation state of +3.75 with low-spin Mn3+ that oxidizes early during charging up to 4.4 V vs. Li+/Li, whereas nickel oxidation occurs subsequently at the 4.5 V plateau.
The primary 4.5 V charge plateau represents a two-phase transition that permanently creates an oxygen-deficient spinel-like phase with a lattice parameter of a = 8.25 Å.
Structural transformation during the first charge is non-reversible, causing all subsequent charge-discharge cycling to take place within the newly formed in situ phase.

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Simonin et al. (2012) studied this question.

synapsesocial.com/papers/6a71c9602163a0a01bc5c836 https://doi.org/10.1039/c2jm31205k

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Implication

Experimental investigation reveals irreversible phase transformation during initial charging of lithium-rich layered oxide cathodes, indicating permanent structural reorganization during cycling.

In situ investigations of a Li-rich Mn–Ni layered oxide for Li-ion batteries

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Cite This Study

In situ investigations of a Li-rich Mn–Ni layered oxide for Li-ion batteries

Discussion

Member takes

Implication

Key Points

Cite This Study

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