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Reactive surface area of the Li-x(Co1/3Ni1/3Mn1/3)O-2 electrode determined by mu+SR and electrochemical measurements

Sugiyama, Jun, Mukai, Kazuhiko, Harada, Masashi, Nozaki, Hiroshi, Miwa, Kazutoshi, Shiotsuki, Taishi, Shindo, Yohei, Giblin, Sean and Lord, James S. 2013. Reactive surface area of the Li-x(Co1/3Ni1/3Mn1/3)O-2 electrode determined by mu+SR and electrochemical measurements. Physical Chemistry Chemical Physics 15 (25) , pp. 10402-10412. 10.1039/C3CP51662H

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Abstract

The self-diffusion coefficient of Li+ ions (DLi) in the positive electrode material Lix(Co1/3Ni1/3Mn1/3)O2 has been estimated by muon-spin relaxation (μ+SR) using powder samples with x = 1–0.49, which were prepared by an electrochemical reaction in a Li-ion battery. Here, since the implanted muons sense a slight change in the internal magnetic field due to Li-diffusion, μ+SR provides an intrinsic DLi through the temperature dependence of the nuclear field fluctuation rate (ν) [Sugiyama et al., Phys. Rev. Lett., 2009, 103, 147601]. Both DLi at 300 K and activation energy (Ea) were estimated to be [similar]2.9 × 10−12 cm2 s−1 and 0.074 eV for the x = 1 sample, [similar]11.0 × 10−12 cm2 s−1 and 0.097 eV for x = 0.70, and [similar]8.9 × 10−12 cm2 s−1 and 0.062 eV for x = 0.49, assuming that the diffusing Li+ ions mainly jump from a regular occupied site to a regular vacant site. The estimated DLi was smaller by roughly one order of magnitude than those for LixCoO2 in the whole x range measured. Furthermore, by making comparison with DLi obtained by electrochemical measurements, the reactive surface area of the Lix(Co1/3Ni1/3Mn1/3)O2 electrode in a liquid electrolyte was found to strongly depend on x particularly at x > 0.8.

Item Type: Article
Status: Published
Schools: Physics and Astronomy
Subjects: Q Science > QC Physics
Publisher: Royal Society of Chemistry
ISSN: 1463-9076
Last Modified: 04 Jun 2017 05:50
URI: http://orca.cf.ac.uk/id/eprint/53979

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