Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Effect of pH on the Synthesis of $LiCoO_2$ with Malonic Acid and Its Charge/Discharge Behavior for a Lithium Secondary Battery

  • Published : 20001100
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Abstract

The pH effect of the precursor solution on the preparation of $LiCoO_2$ by a solution phase reaction containing malonic acid was carried out. Layered $LiCoO_2$ powders were obtained with the precursors prepared at the different pHs (4, 7, and 9) and heat-treated at $700^{\circ}C(LiCoO_2-700)$ or $850^{\circ}C(LiCoO_2-850)$ in air. pHs of the media for precursor synthesis affects the charge/discharge and electrochemical properties of the $LiCoO_2electrodes.$ Upon irrespective of pH of the precursor media, X-ray diffraction spectra recorded for $LiCoO_2-850$ powder showed higher peak intensity ratio of I(003)/I(104) than that of $LiCoO_2-700$, since the better crystallization of the former crystallized better. However, $LiCoO_2$ synthesized at pH 4 displayed an abnormal higher intensity ratio of I(003)/I(104) than those synthesized at pH 7 and 9. The surface morphology of the $LiCoO_2-850$ powders was rougher and more irregular than that of $LiCoO_2-700$ made from the precursor synthesized at pH 7 and 9. The $LiCoO_2electrodes$ prepared with the precursors synthesized at pH 7 and 9 showed a better electrochemical and charge/discharge characteristics. From the AC impedance spectroscopic experiments for the electrode made from the precursor prepared in pH 7, the chemical diffusivity of Li ions (DLi+) in $Li0.58CoO_2determined$ was 2.7 ${\times}$10-8 $cm^2s-1$. A cell composed of the $LiCoO_2-700$ cathode prepared in pH 7 with Lithium metal anode reveals an initial discharge specific capacity of 119.8 mAhg-1 at a current density of 10.0 mAg-1 between 3.5 V and 4.3 V. The full-cell composed with $LiCoO_2-700$ cathode prepared in pH 7 and the Mesocarbon Pitch-based Carbon Fiber (MPCF) anode separated by a Cellgard 2400 membrane showed a good cycleability. In addition, it was operated over 100 charge/discharge cycles and displayed an average reversible capacity of nearly 130 mAhg-1.

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