Formation of Nanosized Defective Lithium Peroxides through Si-Coated Carbon Nanotube Cathodes for High Energy Efficiency Li–O₂ Batteries

The formation and decomposition of lithium peroxides (Li2O2) during cycling is the key process for the reversible operation of lithium–oxygen batteries. The manipulation of such products from the large toroidal particles about hundreds of nanometers to the ones in the scale of tens of nanometers can improve the energy efficiency and the cycle life of the batteries. In this work, we carry out an in situ morphology tuning of Li2O2 by virtue of the surface properties of the n-type Si-modified aligned carbon nanotube (CNT) cathodes. With the introduction of an n-type Si coating layer on the CNT surface, the morphology of Li2O2 formed by discharge changes from large toroidal particles (∼300 nm) deposited on the pristine CNT cathodes to nanoparticles (10–20 nm) with poor crystallinity and plenty of lithium vacancies. Beneficial from such changes, the charge overpotential dramatically decreases to 0.55 V, with the charge plateau lying at 3.5 V even in the case of a high discharge capacity (3450 mA h g–1) being delivered, resulting in the high electrical energy efficiency approaching 80%. Such an improvement is attributed to the fact that the introduction of the n-type Si coating layer changes the surface properties of CNTs and guides the formation of nanosized amorphous-like lithium peroxides with plenty of defects. These results demonstrate that the cathode surface properties play an important role in the formation of products formed during the cycle, providing inspiration to design superior cathodes for the Li–O2 cells.