By James Y. Murdoch, Ying Bai, Khairul Basar, Liquan Chen, Loredana De Rogatis
This booklet is dedicated to the physics, chemistry and fabrics technology of diffusion, mass shipping, and reactivity of solids, together with: physics and chemistry of defects in solids; reactions in and on solids, e.g. intercalation, corrosion, oxidation, sintering; and ion shipping measurements, mechanisms and concept.
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Extra info for Diffusion and Reactivity of Solids
Again, all the characteristic bands of Co2O3 and Co3O4 are observed in the soaked materials, indicating clearly that Co2O3 and Co3O4 are the main produced components in the material, consistent with the results of XRD analysis. Comparing the relative intensities of the spectral peaks of Co2O3 and Co3O4 in the material, we can see that the content of LiCoO2 is lower in Al2O3-coated LiCoO2 than in bare LiCoO2. Meanwhile, it is also found that the content ratio of Co2O3/Co3O4 is higher in Al2O3coated LiCoO2 than in bare LiCoO2, verifying the above proposal.
A reasonable explanation is that fewer Co2+ ions are converted from Co3+ or lost for the Al2O3coated nano-LiCoO2 than for the bare nano-LiCoO2. As Co2+ is stable in liquid while Co3+ is stable in solid, it is proposed that Li+ ion extraction from LiCoO2 and the oxidation of the solvent result in the formation of Co2O3 in Al2O3-coated LiCoO2 and Co3O4 in bare LiCoO2, respectively. This proposal is verified with the following structural characterization of the generated solids by XRD and Raman spectroscopy.
The main generated species have C-O-C and O=C structures. The former, consistent with that of liquid GC-MS results, confirms the existence of poly(ethylene oxide) (PEO)-like polymeric species while the latter demonstrates the formation of carbonates and other carbonyl groups in the liquid. These carbonates might include various solvable (lithium) alkyl carbonates. It is worth pointing out that the vibration bands close (with position difference ≤ ±6cm-1 vs the instrumental resolution of 4cm-1) to that of EC or DMC are not considered in this chapter.