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The electrochemical discharge of VB 2 is a unique process that involves the multiple electron per molecule oxidation of the tetravalent transition metal ion, V (+4 → +5), and each of the two borons 2 × B (−2 → +3), corresponding to a net 11 electron discharge mechanism of the VB 2 /air cell as described by the overall cell reaction: VB 2 + 11/4O 2 → B 2 O 3 + ½ V 2 O 5 . However, in the presence of alkaline electrolytes, the discharge products include alkali salts associated with vanadaic and boric acid. In this study, we used FTIR, XRD, and coulombic efficiency measurements to probe the discharge products of high capacity cells and isolate KVO 3 as the principal vanadium discharge product. Additionally, we show that K 2 B 4 O 7 is the probable borate product. From FTIR analysis in KOH electrolyte, it is evident that the alkaline VB 2 /air discharge reaction is: VB 2 + 11/4O 2 + 2KOH → ½ K 2 B 4 O 7 + KVO 3 + H 2 O. XPS shows that the surface structure of nanoscopic VB 2 is very different from macroscopic VB 2 , which may contribute to the improved electrochemical properties of the nanoscopic material. The understanding of the discharge process and factors affecting performance contribute to furthering the development of extremely high capacity VB 2 /air batteries that utilize multi-electron processes.
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Stuart et al. (2014) studied this question.
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