Mechanochemistry in Sodium Thioantimonate Solid Electrolytes: Effects on Structure, Morphology, and Electrochemical Performance
Bibliographic record
Abstract
Sodium thioantimonate (Na 3 SbS 4 ) and its W-substituted analogue Na 2.88 Sb 0.88 W 0.12 S 4 have been identified as potential electrolyte materials for all-solid-state sodium batteries due to their high Na + conductivity. Ball milling mechanochemistry is a frequently employed synthetic approach to produce such Na + -conductive solid solutions; however, changes in the structure and morphology introduced in these systems via the mechanochemistry process are poorly understood. Herein, we combined X-ray absorption fine structure spectroscopy, Raman spectroscopy, solid-state nuclear magnetic resonance spectroscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy characterization techniques to provide an in-depth analysis of these solid electrolytes. We report unique changes seen in the structure and morphology of Na 3 SbS 4 and Na 2.88 Sb 0.88 W 0.12 S 4 resulting from ball milling, inducing changes in the electrochemical performance of the solid-state batteries. Specifically, we observed a tetragonal-to-cubic crystal phase transition within Na 3 SbS 4 following the ball mill, resulting in an increase in Na + conductivity. In contrast, the Na + conductivity was reduced in mechanochemically treated Na 2.88 Sb 0.88 W 0.12 S 4 due to the formation and accumulation of a WS 2 phase. In addition, mechanochemical treatment alters the surface morphology of densified Na 2.88 Sb 0.88 W 0.12 S 4 pellets, providing intimate contact at the solid electrolyte/Na interface. This phenomenon was not observed in Na 3 SbS 4 . This work reveals the structural and morphological origin of the changes seen in these materials’ electrochemical performance and how mechanochemical synthesis can introduce them.
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How this classification was reachedexpand
Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| 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) | 0.000 | 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 teacher head, 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".