Investigation of Fluorophosphate Cathode Materials for Na Ion Batteries By Ex Situ <sup>23</sup> Na Solid-State Nuclear Magnetic Resonance
Bibliographic record
Abstract
Sodium ion batteries have experienced a renaissance in recent years owing to the low cost and high abundance of sodium relative to lithium resources.1 Despite this renewed attention, there remains a need to realize sodium electrode materials that are suitable for commercial applications. In light of this, there is significant motivation to identify and analyze various properties of novel electrode materials, including structural and ion diffusion changes that occur during the electrochemical cycling process. Solid-state nuclear magnetic resonance (ssNMR) is implemented here in an attempt to characterize structure and site-specific ion mobility in the fluorophosphate family of cathode materials (Na2MPO4F), as they are known to exhibit high thermal and electrochemical stability.2,3 Ex situ 23Na NMR studies at fast magic angle spinning (65 kHz) allow for sufficient spectral resolution to observe local changes at unique Na environments in these paramagnetic electrode materials. Na atoms housed in the two crystallographically unique positions in the layered Na2FePO4F phase are distinguishable via this technique (Figure 1a), offering the opportunity to probe local properties in the pristine phase. Further, by incorporation of this material into a sodium ion cell, the changes to the 23Na NMR spectrum can be correlated ex situ to structural changes directly resulting from the electrochemical (de)intercalation process. The appearance and relative increase of two new Na peaks in the NMR spectrum (Figure 1b) upon electrochemical desodiation of the material suggests that Na atoms in both crystallographic environments may in fact be mobile despite an apparent lack of chemical exchange between sites. These new Na resonances can be assigned to the partially oxidized variant of the pristine material, where the dramatic shift in peaks in the NMR spectrum is attributed to the change in electron configuration of the transition metal from Fe2+ to Fe3+. Ongoing efforts to quantify the diffusion of Na ions and characterize the mechanism of electrochemical desodiation will be presented. References: (1) Palomares, V.; Serras, P.; Villaluenga, I.; Hueso, K. B.; Carretero-González, J.; Rojo, T. Energy Environ. Sci. 2012, 5(3), 5884. (2) Ellis, B. L.; Makahnouk, W. R. M.; Rowan-Weetaluktuk, W. N.; Ryan, D. H.; Nazar, L. F. Chem. Mater. 2010, 22(3), 1059. (3) Ellis, B. L.; Makahnouk, W. R. M.; Makimura, Y.; Toghill, K.; Nazar, L. F. Nat. Mater. 2007, 6 (10), 749. Figure 1
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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 | 0.001 | 0.001 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.001 | 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".