Symmetry Breaking Enabled Stable Oxygen Redox in Li‐Rich Cathodes via π‐Type Interaction
Bibliographic record
Abstract
Abstract Effectively stabilizing oxygen redox is the most challenging task for the practical applications of high‐energy‐density Li‐rich cathode materials. However, how to accurately tune the oxygen energy level to achieve reversible redox remains puzzling so far. In this work, we achieve stable oxygen redox in layered Li‐rich materials over the whole voltage range without irreversible O2 release by adjusting the interlayer metal cation environment adjacent to the ligand. Combining synchrotron X‐ray absorption spectroscopy and theoretical analysis of metal‐ligand orbital combinations, we confirm the obvious charge transfer from O to Ni due to the π‐type interaction between Ni 3d spin‐down t2g orbitals and O 2p orbitals. Furthermore, Ab initio molecular dynamics simulations reveal the spontaneous symmetry breaking of the Ni coordination environment after Li extraction under the π‐type interaction, which enhances the intrinsic competition between anion and cation oxidation, keeping π* state (from O 2p splitting) below the metal band to avoid over‐oxidation. As a result, the modified material shows improved electrochemical performance and stable structural/interface evolution. This work provides new insights into the relationship between the adjacent metal environment and the ligand O redox reactions.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.001 | 0.000 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".