Excavating Anomalous Capacity Increase of Li–S Pouch Cells by Electrochemical Oscillation Formation

The insufficient activation of a S/C cathode makes insufficient utilization of S in Li–S pouch cells, while the deep activation of a S/C cathode in a formation process is time-consuming and produces lithium polysulfides, which corrode a Li anode. Both situations lead to a low actual capacity of the Li–S pouch cells with a high S loading but are ignored for coin cells. In this work, electrochemical oscillation (EOS) formation employing hundreds of shallow discharge/charge cycles with high frequency was used to replace the resting and/or one deep discharge/charge cycle of traditional (TD) formation protocols. By controlling the discharge/charge capacity separately, symmetric oscillation (SOS) and asymmetric oscillation (ASOS) protocols were performed to facilitate the infiltration of electrolyte into the S cathode and restrict the formed lithium polysulfide in the cathode region. For SOS formation, the batteries were discharged/charged above 2.4 V with the same (symmetric) capacity with 2.78 × 10–3 Hz of oscillation frequency (∼1.4 mAh/g for SOS-500), in which the polysulfide dissolution was suppressed effectively. For ASOS formation, 100% discharge capacity (also ∼1.4 mAh/g for ASOS-500) and 92% charge capacity are set in each oscillation period, which leads to better activation effect but more shuttling polysulfides than SOS. Compared with SOS protocol, for ASOS protocol, more oxidative S (instead of polysulfides) inside original nonactivated cathode will be preferentially reduced in the next discharging process, but all the accumulated polysulfides during discharge of activation are oxidized into elemental S in the final charging process. These efficient formation protocols increase the practical capacity by up to 160% after 50 cycles without any change in pouch cell assembly.