Unravelling high volumetric capacity of Co3O4 nanograin-interconnected secondary particles for lithium-ion battery anodes

The development of high-tap density electrode materials that can simultaneously achieve stable electrochemical performance at high charge/discharge rates is critically in demand. Herein, we propose an innovative material design that can offer high tap density and excellent rate capabilities by using Co3O4 nanograin-interconnected secondary particles (Co3O4 NISPs). By taking advantage of a conversion reaction that forms Co from Co3O4, we demonstrate that Co3O4 NISPs are capable of creating a number of metallic Co sites along with a number of vacant sites in-between nanograins. Electrochemical tests that reveal reduced internal cell resistance and more accessible Li diffusion are achieved for Co3O4 NISPs compared with Co3O4 nanoparticles (NPs). Additionally, in situ X-ray diffraction (XRD) analyses, electron energy loss spectroscopy (EELS), and density functional theory (DFT) calculations reveal that the insulating intermediate product (CoO) is formed less on the Co3O4 NISPs, which can enhance the charge transport. Attributed to the combinatorial effects of Co3O4 nanograins that form metallic Co upon conversion and secondary particles that enable high tap density, Co3O4 NISPs show the most outstanding volumetric capacity (2167.3 mA h cm−3 at a current density of 500 mA g−1) among spinel-type metal oxide electrode materials researched so far.