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 exhi...

Nonaqueous solvents in modern battery technologies undergo electroreduction at negative electrodes, leading to the formation of a solid-electrolyte interphase (SEI). The mechanisms and reactions leading to a stable SEI on silicon electrodes in lithium-ion batteries are still poorly understood. This lack of understanding inhibits the rational design of electrolyte additives, active material coatings, and the prediction of Li-ion battery life in general. We prepared SEI with a common nonaqueous solvent (LiPF6 in PC and in EC/DEC 1:1 by wt %) on silicon oxide and etched silicon (001) surfaces in various states of lithiation to understand the role of surface chemistry on the SEI formation mechanism and SEI structure. Anhydrous and anoxic techniques were used to prevent air and moisture contamination of prepared SEI films, allowing for more accurate characterization of SEI chemical stratification and composition by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (TOF-SIMS) depth profiling. Additionally, multivariate statistical methods were used to better understand TOF-SIMS depth profiling studies. We conclude that the absence of native-oxide layer on silicon has a significant impact on the formation, composition, structure, and thickness of the SEI.

The lithium insertion behavior of nanoparticle (3-D) and nanosheet (2-D) architectures of TiO2(B) is quite different, as observed by differential capacity plots derived from galvanostatic charging/discharge experiments. DFT+U calculations show unique lithiation mechanisms for the different nanoarchitectures. For TiO2(B) nanoparticles, A2 sites near equatorial TiO6 octahedra are filled first, followed by A1 sites near axial TiO6 octahedra. No open-channel C site filling is observed in the voltage range studied. Conversely, TiO2(B) nanosheets incrementally fill C sites, followed by A2 and A1. DFT+U calculations suggest that the different lithiation mechanisms are related to the elongated geometry of the nanosheet along the a-axis that reduces Li+–Li+ interactions between C and A2 sites. The calculated lithiation potentials and degree of filling agree qualitatively with the experimentally observed differential capacity plots.

Li 2 MoO 3 , with a Mo(IV)/Mo(VI) redox couple, has been tested as a cathode additive to make lithium-ion batteries safe under abnormal discharge conditions. Its high charging capacity and sloping discharge voltage below 3.4 V vs Li + /Li effectively prevents the Cu anode current collector from oxidative dissolution at the overdischarge condition. However, molybdenum dissolution from the electrochemically charged Li 2 MoO 3 quickly deteriorates the battery performance at 45°C. A solid solution of Li 2 MoO 3 with LiFeO 2 has stabilized the crystalline structure at the charged states and suppressed the Mo(VI) dissolution. The addition of 10 wt % 0.9Li 2 MoO 3 −0.1LiFeO 2 to LiCoO 2 electrode enables long-term, high-temperature cycling in the operating voltage range of 0.0−4.3 V vs graphite.