Revealing the Thermal Safety of Prussian Blue Cathode for Safer Nonaqueous Batteries

Li, Zheng; Dadsetan, Mehran; Gao, Junxian; Zhang, Sensen; Cai, Lirong; Naseri, Ali; Jimenez‐Castaneda, Martha E.; Filley, Timothy; Miller, Jeffrey T.; Thomson, Murray J.; Pol, Vilas G.

doi:10.1002/aenm.202101764

Title: Revealing the Thermal Safety of Prussian Blue Cathode for Safer Nonaqueous Batteries

Journal Article · 05 October 2021 · Advanced Energy Materials

DOI: https://doi.org/10.1002/aenm.202101764 · OSTI ID:1824892

Li, Zheng ^[1]; Dadsetan, Mehran ^[2]; Gao, Junxian ^[1]; Zhang, Sensen ^[1]; Cai, Lirong ^[1]; Naseri, Ali ^[2]; Jimenez‐Castaneda, Martha E. ^[3]; Filley, Timothy ^[3]; Miller, Jeffrey T. ^[1]; Thomson, Murray J. ^[2];

^[1]

Davidson School of Chemical Engineering Purdue University West Lafayette IN 47907 USA
Department of Mechanical &, Industrial Engineering University of Toronto Toronto ON M5S 3G8 Canada
Department of Earth Atmospheric, and Planetary Sciences Purdue University West Lafayette IN 47907 USA

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 O ₂ 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 LiCoO ₂ –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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Sponsoring Organization:: USDOE

OSTI ID:: 1824892

Journal Information:: Advanced Energy Materials, Journal Name: Advanced Energy Materials Journal Issue: 42 Vol. 11; ISSN 1614-6832

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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