Lithium Insertion in Nanostructured TiO2(B) Architectures

Abstract

Electric vehicles and grid storage devices have potentialto become feasible alternatives to current technology, but only if scientists can develop energy storage materials that offer high capacity and high rate capabilities. Chemists have studied anatase, rutile, brookite and TiO₂(B) (bronze) in both bulk and nanostructured forms as potential Li-ion battery anodes. In most cases, the specific capacity and rate of lithiation and delithiation increases as the materials are nanostructured. Scientists have explained these enhancements in terms of higher surface areas, shorter Li⁺ diffusion paths and different surface energies for nanostructured materials allowing for more facile lithiation and delithiation. Of the most studied polymorphs, nanostructured TiO₂(B) has the highest capacity with promising high rate capabilities. TiO₂(B) is able to accommodate 1 Li⁺ per Ti, giving a capacity of 335 mAh/g for nanotubular and nanoparticulate TiO₂(B). The TiO₂(B) polymorph, discovered in 1980 by Marchand and co-workers, has been the focus of many recent studies regarding high power and high capacity anode materials with potential applications for electric vehicles and grid storage. This is due to the material’s stability over multiple cycles, safer lithiation potential relative to graphite, reasonable capacity, high rate capability, nontoxicity, and low cost (Bruce, P. G.; Scrosati, B.; Tarascon, J.-M. Nanomaterials for Rechargeable Lithium Batteries. Angew. Chem., Int. Ed.2008, 47, 2930–2946). One of the most interesting properties of TiO₂(B) is that both bulk and nanostructured forms lithiate and delithiate through a surface redox or pseudocapacitive charging mechanism, giving rise to stable high rate charge/discharge capabilities in the case of nanostructured TiO₂(B). When other polymorphs of TiO₂ are nanostructured, they still mainly intercalate lithium through a bulk diffusion-controlled mechanism. TiO₂(B) has a unique open crystal structure and low energy Li⁺ pathways from surface to subsurface sites, which many chemists believe to contribute to the pseudocapacitive charging. Several disadvantages exist as well. TiO₂(B), and titania in general, suffers from poor electronic and ionic conductivity. Nanostructured TiO₂(B) also exhibits significant irreversible capacity loss (ICL) upon first discharge (lithiation). Nanostructuring TiO₂(B) can help alleviate problems with poor ionic conductivity by shortening lithium diffusion pathways. Unfortunately, this also increases the likelihood of severe first discharge ICL due to reactive Ti–OH and Ti–O surface sites that can cause unwanted electrolyte degradation and irreversible trapping of Li⁺. Nanostructuring also results in lowered volumetric energy density, which could be a considerable problem for mobile applications. We will also discuss these problems and proposed solutions. Scientists have synthesized TiO₂(B) in a variety of nanostructures including nanowires, nanotubes, nanoparticles, mesoporous-ordered nanostructures, and nanosheets. Many of these structures exhibit enhanced Li⁺ diffusion kinetics and increased specific capacities compared to bulk material, and thus warrant investigation on how nanostructuring influences lithiation behavior. This Account will focus on these influences from both experimental and theoretical perspectives. We will discuss the surface charging mechanism that gives rise to the increased lithiation and delithiation kinetics for TiO₂(B), along with the influence of dimensional confinement of the nanoarchitectures, and how nanostructuring can change the lithiation mechanism considerably.