Arseni V. Ushakov

Diffusion aspects of lithium intercalation as applied to the development of electrode materials for lithium-ion batteries

The creation of new electrode materials and the modification of existing ones are important trends in the development of lithium-ion batteries. Of special significance is to evaluate their diffusivity, i.e., the ability of providing transfer of the electroactive component. Such electrochemical techniques as cyclic voltammetry, electrochemical impedance spectroscopy, potentiostatic intermittent titration technique, and galvanostatic intermittent titration technique are used for this purpose. The values of chemical diffusion coefficient D estimated in similar electrode materials are shown to scatter by several orders of magnitude. Principal causes of this rather considerable scattering are discussed, including the uncertainty of diffusion area estimations and the use of various approaches to deriving equations to calculate D. Our conclusions are illustrated by examples of D estimations in the electrode materials LixC6, LixSn, LixTiO2, LixWO3, LiMyMn2−yO4, and LiFePO4.

Models of lithium transport as applied to determination of diffusion characteristics of intercalation electrodes

In order to elucidate the mechanism of lithium transport in intercalation electrodes based on solid lithium-accumulating compounds and determine its parameters, the kinetic models are used which allow the combined analysis of electrode impedance spectroscopy, cyclic voltammetry, pulse chronoampero- and chronopotentiometry data to be carried out. The models describe the stages of consecutive lithium transport in the surface layer and bulk of electrode-material particles, including the accumulation of species in the bulk. The lithium transport stages that occur in the surface layer of an intercalation-material particle and in its bulk are both of the diffusion nature but substantially differ as regards their characteristic times and diffusion coefficients D. Taking account of this peculiarity and assessing adequately the geometrical configuration of intercalation system allow the diffusion parameters of lithium transport to be correctly determined.

The synthesis, structure, and electrochemical properties of Li2FeSiO4-based lithium-accumulating electrode material

Different approaches to synthesis of Li2FeSiO4-based electrode materials for lithium intercalation, using low-cost and abundant Li-, Si-, and Fe-containing parent substances, are discussed. XRD, SEM, and a laser-diffraction analyzer of particle size were used for structure and morphology characterization of the composite electrode materials. Li2FeSiO4 was shown to be the main lithium-accumulating crystalline phase; minor LiFeO2 and Li2SiO3 admixtures are also present. The material microparticles’ average size was shown to vary from tenths of micrometer to 1 μm. Larger objects sized ca. 2–4 μm are the microparticles’ agglomerates. The material electrochemical properties were studied by dc chronopotentiometry (galvanostatic charging–discharging) and cyclic voltammetry with potential linear sweeping. The initial reversible cycled capacity of the best samples is 170 mA h/g. The anodic and cathodic processes manifest obvious hysteresis caused by the presence of several different lithium ion energy states in the material; the transition between the states is kinetically hindered. The dependences of the specific capacity and its stability under cycling on the current load and the conductive carbon component content in the composite were elucidated.

Separate Determination of Borohydride, Borate, Hydroxide, and Carbonate in the Borohydride Fuel Cell by Acid-Base and Iodometric Potentiometric Titration

A methodology for quantitative chemical analysis of the complex “borohydride-borate-hydroxide-carbonate-water” mixtures used as fuel in the borohydride fuel cell was developed and optimized. The methodology includes the combined usage of the acid-base and iodometric titration methods. The acid-base titration method, which simultaneously uses the technique of differentiation and computer simulation of titration curves, allows one to determine the contents of hydroxide (alkali), carbonate, and total “borate