Improved electrode characteristics of olivine-LiCoPO4 processed by high energy milling

Olivine-LiCoPO4 powders have been processed by mechanical grinding for time periods ranging from 0.5 to 10 h with conductive carbon contents of 0, 8 and 20% (w/w). In all cases the grinding process produces an amorphization of the crystalline materials and decreases both the crystallite and particle sizes. Secondary phases are detected by scanning electron microscopy and X-ray diffraction in the materials milled for times greater than 2 h without carbon. The addition of conductive carbon during the milling process decelerates the degradation of the material and secondary phases are not detected even after 10 h of grinding. The electrochemical performance of olivine-LiCoPO4 is improved in all the materials milled for 0.5 h; a lower cell polarization and a larger reversible specific capacity are observed. These characteristics are enhanced in the materials grinded with conductive carbon, which also display a capacity retention with cycling clearly superior to that of the fresh LiCoPO4. Ball milling LiCoPO4 for times greater than 1 h is detrimental for the response of the electrode, independently on the amount of conductive carbon in the grinding media.