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Sodium thioantimonate (Na 3 SbS 4 ) is an attractive solid-state electrolyte for sodium-ion batteries due to its high ionic conductivity and stability in protic solvents. Herein, we describe solution-based routes for its synthesis. First, we demonstrate the synthesis of the Sb 2 S 3 precursor via thermodynamically favorable metathesis between Na 2 S and SbCl 3 . This solution-based approach is further extended to couple the resulting Sb 2 S 3 with Na 2 S for the synthesis of Na 3 SbS 4 . It is shown that ethanol is a superior solvent to water for solution-based synthesis of Na 3 SbS 4 with respect to yield, morphology, and performance. Amorphous Sb 2 S 3 synthesized from low-temperature metathesis produced highly crystalline Na 3 SbS 4 with a room temperature Na + conductivity of 0.52 mS cm −1 and low activation energy, comparable to leading values reported in the literature.
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Enhancing Cycle Life in Superoxide‐Based Na–O 2 Batteries by Reducing Interface Reactivity
Abstract Sodium–oxygen (Na–O2) batteries are considered a promising energy storage alternative to current state‐of‐the‐art technologies owing to their high theoretical energy density, along with the natural abundance and low price of Na metal. The chemistry of these batteries depends on sodium superoxide (NaO2) or peroxide (Na2O2) being formed/decomposed. Most Na–O2batteries form NaO2, but reversibility is usually quite limited due to side reactions at interfaces. By using new materials, including a highly active catalyst based on vanadium phosphide (VP) nanoparticles, an ether/ionic liquid‐based electrolyte, and an effective sodium bromide (NaBr) anode protection layer, the sources of interface reactivity can be reduced to achieve a Na–O2battery cell that is rechargeable for 1070 cycles with a high energy efficiency of more than 83%. Density functional theory calculations, along with experimental characterization confirm the three factors leading to the long cycle life, including the effectiveness of the NaBr protective layer on the anode, a tetraglyme/EMIM‐BF4based electrolyte that prevents oxidation of the VP cathode catalyst surface, and the EMIM‐BF4ionic liquid aiding in avoiding electrolyte decomposition on NaO2.
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- Award ID(s):
- 2312359
- PAR ID:
- 10571703
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Energy Materials
- Volume:
- 15
- Issue:
- 20
- ISSN:
- 1614-6832
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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