A Lithium-ion Battery Using Partially Lithiated Graphite Anode and Amphi-redox LiMn2O4 Cathode.

Delithiation followed by lithiation of Li+-occupied (n-type) tetrahedral sites of cubic LiMn2O4 spinel (LMO) at ~4 [Formula: see text] (delivering ~100 mAh gLMO-1) has been used for energy storage by lithium ion batteries (LIBs). In this work, we utilized unoccupied (p-type) octahedral sites of LMO available for lithiation at ~3 [Formula: see text] (delivering additional ~100 mAh gLMO-1) that have never been used for LIBs in full-cell configuration. The whole capacity of amphi-redox LMO, including both oxidizable n-type and reducible p-type redox sites, at ~200 mAh gLMO-1 was realized by using the reactions both at 4 [Formula: see text] and 3 [Formula: see text]. Durable reversibility of the 3 V reaction was achieved by graphene-wrapping LMO nanoparticles (LMO@Gn). Prelithiated graphite (LinC6, n < 1) was used as anodes to lithiate the unoccupied octahedral sites of LMO for the 3 V reaction.

Doubling the capacity of lithium manganese oxide spinel by a flexible skinny graphitic layer.

By coating nanoparticular lithium manganese oxide (LMO) spinel with a few layers of graphitic basal planes, the capacity of the material reached up to 220 mA h g(-1) at a cutoff voltage of 2.5 V. The graphitic layers 1) provided a facile electron-transfer highway without hindering ion access and, more interestingly, 2) stabilized the structural distortion at the 3 V region reaction. The gain was won by a simple method in which microsized LMO was ball-milled in the presence of graphite with high energy. Vibratory ball milling pulverized the LMO into the nanoscale, exfoliated graphite of less than 10 layers and combined them together with an extremely intimate contact. Ab initio calculations show that the intrinsically very low electrical conductivity of the tetragonal phase of the LMO is responsible for the poor electrochemical performance in the 3 V region and could be overcome by the graphitic skin strategy proposed.