Crystal Structure and Electrochemical Properties of A<sub>2</sub>MPO<sub>4</sub>F Fluorophosphates (A = Na, Li; M = Fe, Mn, Co, Ni)
Bibliographic record
Abstract
We report new solid state and hydrothermal synthetic routes to (Li,Na) 2 FePO 4 F that incorporate carbon-containing additives and result in good electrochemical properties of this Li (or Na) ion electrode material. Single crystal X-ray diffraction analysis of Na 2 FePO 4 F prepared by flux growth confirms the unusual structural features of this compound that include pairs of face-sharing metal octahedra and [6 + 1] coordination of the sodium ions. Facile Na−Li ion-exchange occurs upon reflux with lithium salts, upon electrochemical cycling in a cell (vs. Li), and also in a cell simply equilibrated at OCV. The material does not exhibit typical two-phase behavior on electrochemical cycling. A combination of a redox process which occurs with little structural strain, and ion scrambling give rise to a solid solution-like sloping voltage profile on charge−discharge, although localization of the Fe 2+/3+ in the mixed valence single phase intermediate, Na 1.5 FePO 4 F drives a very small structural distortion. Temperature-dependent Mössbauer spectroscopy measurements confirm this localization, at least on short time scales (10 −8 s), which persists to 370 °C. Finally, polycrystalline powders of other members of this family of compounds (Na 2 CoPO 4 F, Na 2 NiPO 4 F) were synthesized for the first time. Na 2 CoPO 4 F has a Co 2+ /Co 3+ potential near 4.8 V. Mixed-metal phosphates of the form Na 2 (Fe 1− x M x )PO 4 F, where M = Co, Mg, were also synthesized and found to be promising positive electrode materials for Li-ion or Na-ion energy storage devices.
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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".