Rational design of oxide/carbon composites to achieve superior rate-capability via enhanced lithium-ion transport across carbon to oxide

Abstract

Coating oxides with conductive carbon is a widely used strategy to improve the rate capability of oxides by enhancing their electronic conductivity. However, there is a growing concern that a carbon layer may hinder lithium-ion transport to oxides, thus limiting the rate capability. Nonetheless, this issue has not yet been thoroughly investigated, and whether lithium-ion transport across a carbon layer does indeed limit the rate capability remains unclear. To single out the effect of lithium-ion transport across a carbon layer on the rate capability, we propose the rational design and synthesis of nano-perforated graphene (NPG)-wrapped oxide composites using commercial Li₄Ti₅O₁₂ (LTO) and LiFePO₄ (both with a particle diameter of ∼70 nm), wherein the NPG has nano-perforations on the basal plane of graphene. As the number of nano-perforations in the composites increases, the rate capability significantly increases. For example, NPG-wrapped LTO shows a specific capacity of 117.9 mA h g⁻¹ at 100C and could be stably charged–discharged even at 300C. The excellent rate capability is mainly due to the enhancement of lithium-ion transport through the nano-perforations of NPG. Cyclic voltammetry and impedance analyses reveal that the improved rate capability of NPG-wrapped LTO is closely associated with an increase in the area of electrochemically active sites of LTO in the composite due to the enhanced lithium-ion transport through the nano-perforations of NPG, indicating that lithium-ion transport across a carbon layer could limit the rate capability of oxides coated with highly conductive carbon. These salient results will provide further impetus to the design and synthesis of novel high-rate carbon-coated oxides.