Fast discharge process of layered cobalt oxides due to high Na⁺ diffusion

Sodium ion secondary battery (SIB) is a low-cost and ubiquitous secondary battery for next-generation large-scale energy storage. The diffusion process of large Na(+) (ionic radius is 1.12 Å), however, is considered to be slower than that of small Li(+) (0.76 Å). This would be a serious disadvantage...

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Bibliographic Details
Published in:Scientific reports 2015-03, Vol.5 (1), p.9006-9006, Article 9006
Main Authors: Shibata, Takayuki, Fukuzumi, Yuya, Kobayashi, Wataru, Moritomo, Yutaka
Format: Article
Language:English
Subjects:
Cobalt
Diffusion
Energy storage
Lithium
Oxides
Phase transitions
Sodium
Spectroscopy
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Summary:Sodium ion secondary battery (SIB) is a low-cost and ubiquitous secondary battery for next-generation large-scale energy storage. The diffusion process of large Na(+) (ionic radius is 1.12 Å), however, is considered to be slower than that of small Li(+) (0.76 Å). This would be a serious disadvantage of SIB as compared with the Lithium ion secondary battery (LIB). By means of the electrochemical impedance spectroscopy (EIS), we determined the diffusion constant (D) of Na(+) in thin films of O3- and P2-type NaCoO2 with layered structures. We found that the D values (~ 0.5-1.5 × 10(-10) cm(2)/s) of Na(+) are higher than those (< 1 × 10(-11) cm(2)/s) of Li(+) in layered LiCoO2. Especially, the D values of O3-NaCoO2 are even higher than those of P2-NaCoO2, probably because O3-NaCoO2 shows successive structural phase transitions from the O3, O'3, P'3, to P3 phases with Na(+) deintercalation. We further found that the activation energy (ED ~ 0.4 eV) for the Na(+) diffusion is significantly low in these layered cobalt oxides. We found a close relation between the relative capacity and the renormalized discharge rate ( = L(2)/DT, where L and T are the film thickness and discharge time, respectively).
ISSN:2045-2322
2045-2322
DOI:10.1038/srep09006