The self-diffusion coefficient of Li(+) ions (D(Li)) in the positive electrode material Li(x)(Co(1/3)Ni(1/3)Mn(1/3))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 D(Li) through the temperature dependence of the nuclear field fluctuation rate (ν) [Sugiyama et al., Phys. Rev. Lett., 2009, 103, 147601]. Both D(Li) at 300 K and activation energy (E(a)) were estimated to be ∼2.9 × 10(-12) cm(2) s(-1) and 0.074 eV for the x = 1 sample, ∼11.0 × 10(-12) cm(2) s(-1) and 0.097 eV for x = 0.70, and ∼8.9 × 10(-12) cm(2) 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 D(Li) was smaller by roughly one order of magnitude than those for Li(x)CoO2 in the whole x range measured. Furthermore, by making comparison with D(Li) obtained by electrochemical measurements, the reactive surface area of the Li(x)(Co(1/3)Ni(1/3)Mn(1/3))O2 electrode in a liquid electrolyte was found to strongly depend on x particularly at x > 0.8.
In this study, electron irradiation effects on lithium peroxide (Li 2 O 2 ), which is an important discharge product of Li-air (or Li-O 2 ) batteries, were investigated using selected-area electron diffraction (SAED) and high-energy resolution electron energy-loss spectroscopy (EELS). The results obtained show that Li 2 O 2 to Li 2 O transformation occurs with 80 and 300 keV incident electrons under high electron dose rates at 20 and %183 °C. The Li 2 O 2 to Li 2 O transformation rate for 300 keV was 1/5 of that for 80 keV with the irradiation taking place at %183 °C. We also present a series of the EELS spectra that can be used as a criterion to judge the molar ratio of Li 2 O to Li 2 O 2 in the general systems where Li 2 O 2 and Li 2 O coexist.
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