Journal
JOURNAL OF PHYSICAL CHEMISTRY C
Volume 117, Issue 39, Pages 19875-19884Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp406626x
Keywords
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Funding
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences
- U.S. National Science Foundation [1006568]
- Direct For Mathematical & Physical Scien
- Division Of Materials Research [1006568] Funding Source: National Science Foundation
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The superiron salts BaFeO4 and K2FeO4 when utilized as battery cathodes both undergo a three electron charge transfer; however, they exhibit significantly different physical and electrochemical properties. K2FeO4 exhibits higher solid-state stability and higher intrinsic 3e(-) capacity (406 mAh/g) than BaFeO4 (313 mAh/g); however, the rate of cathodic charge transfer is considerably higher for BaFeO4. To understand these differences, primary coin cells of alkaline batteries containing either mu m-BaFeO4, mu m-K2FeO4, or nm-K2FeO4 (nm = nanometer, or mu m = micrometer size particles) were constructed and discharged to various depths under a constant load. Discharged cathode composite were studied by ex-situ X-ray absorption measurements. The oxidation state of discharge product of the Fe local symmetry was followed by the magnitude of K-edge and pre-edge Fe 1s to 3d peak. To track structural changes, the extended X-ray absorption fine structure (EXAFS)chi functions of the partially discharged cathodes were subject to linear combination fitting. The expanded BaFeO4 lattice, or the much larger surface-electrolyte interface in the nm-K2FeO4 materials, significantly increased their capacities compared to mu m-K2FeO4. In the case of nm-K2FeO4, electron density is more distributed by water intercalation about the Fe hydrous environment, which relieves the stress of full Fe6+ to Fe3+ reduction. The stronger Ba-FeO4 anion-cation interaction and increased lattice size apparently slows the rate of lattice rearrangement into the discharge product.
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