Is small particle size more important than carbon coating? An example study on LiFePO4 cathodes

Based on careful analysis of nine papers by different research groups, we show, for the first time, that in LiFePO4-based cathode materials the electrode resistance depends solely on the mean particle size. The effect of carbon coating is marginal, it suffices that each LiFePO4 particle is point-contacted with a reasonable number of carbon black particles usually added in the course of electrode preparation. We present a simple but general theoretical model that consistently explains this unexpected result. The main reason for the relatively small importance of carbon coatings is the fact that the ionic conductivity (ca. 10−11–10−10 S cm−1 at RT) is much smaller than the electronic (>10−9 S cm−1 at RT). The present finding could be of significant importance not only for further optimization of LiFePO4 cathodes, but also for preparation of other cathode materials in which the ionic conductivity is much lower than the electronic.