Revealing the Thermal Safety of Prussian Blue Cathode for Safer Nonaqueous Batteries
Bibliographic record
Abstract
Abstract Prussian blue analogs (PBAs) are promising cathode materials for many next‐generation metal‐ion batteries due to their exceptional electrochemical performance. Their oxygen‐free structure avoids a common battery thermal runaway pathway which requires O2 liberation. Herein, the thermal runaway mechanisms of PBAs are studied from the level of material and full cell in nonaqueous sodium‐ and potassium‐ion batteries (SIBs and KIBs). Their hidden safety issue and a novel runaway mechanism that requires no oxygen evolution are identified. The cyanide groups are released (≈51.4 wt%) as toxic cyanides above 200 °C, which also exothermically react with the electrolyte and cause the runaway. The cyanide gas generation mechanism is proposed as cathode hydrolytic disproportionation by Raman spectroscopy, X‐ray photoelectron spectroscopy, in situ environmental transmission electron microscopy, and operando synchrotron X‐ray diffraction studies. In addition, full‐cell level calorimetric studies reveal mitigated heat generation but lower initiation temperature of runaway from such SIBs and KIBs than conventional LiCoO2–graphite system. These results change how PBA materials are evaluated from a safety standpoint, suggesting that they cannot be regarded as safe cathodes. They also indicate the correlations between thermal safety and their crystal defects or trapped water content. The proposed thermal runaway mechanism provides insights to assist in the building of safer next‐generation batteries.
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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".