Wojciech Zając

Structural, Transport and Electrochemical Properties of LiFePO4 Substituted in Lithium and Iron Sublattices (Al, Zr, W, Mn, Co and Ni)

LiFePO4 is considered to be one of the most promising cathode materials for lithium ion batteries for electric vehicle (EV) application. However, there are still a number of unsolved issues regarding the influence of Li and Fe-site substitution on the physicochemical properties of LiFePO4. This is a review-type article, presenting results of our group, related to the possibility of the chemical modification of phosphoolivine by introduction of cation dopants in Li and Fe sublattices. Along with a synthetic review of previous papers, a large number of new results are included. The possibility of substitution of Li+ by Al3+, Zr4+, W6+ and its influence on the physicochemical properties of LiFePO4 was investigated by means of XRD, SEM/EDS, electrical conductivity and Seebeck coefficient measurements. The range of solid solution formation in Li1−3xAlxFePO4, Li1−4xZrxFePO4 and Li1−6xWxFePO4 materials was found to be very narrow. Transport properties of the synthesized materials were found to be rather weakly dependent on the chemical composition. The battery performance of selected olivines was tested by cyclic voltammetry (CV). In the case of LiFe1−yMyPO4 (M = Mn, Co and Ni), solid solution formation was observed over a large range of y (0 < y ≤ 1). An increase of electrical conductivity for the substitution level y = 0.25 was observed. Electrons of 3d metals other than iron do not contribute to the electrical properties of LiFe1−yMyPO4, and substitution level y > 0.25 leads to considerably lower values of σ. The activated character of electrical conductivity with a rather weak temperature dependence of the Seebeck coefficient suggests a small polaron-type conduction mechanism. The electrochemical properties of LiFe1−yMyPO4 strongly depend on the Fe substitution level.

Applicability of Gd-doped BaZrO3, SrZrO3, BaCeO3 and SrCeO3 proton conducting perovskites as electrolytes for solid oxide fuel cells

AbstractFour proton conducting oxides of perovskite structure: BaZrO3, SrZrO3, BaCeO3 and SrCeO3 doped with 5 mol.% of gadolinium are compared in terms of crystal structure, microstructure, sinterability, water sorption ability, ionic transference number, electrical conductivity and stability towards CO2. Relations between proton conductivity, structural and chemical parameters: pseudo-cubic unit cell volume, lattice free volume, tolerance factor, crystal symmetry and electronegativity are discussed. The grain boundary resistance is shown to be the limiting factor of total proton-conductivity for the materials examined. The highest proton conductivity was observed for BaCeO3, however, it turned out to be prone to degradation in CO2-containing atmosphere and reduction at high temperatures. On the other hand, Ba and Sr zirconates are found to be more chemically stable, but exhibit low electrical conductivity. Electrical conductivity relaxation upon hydration is used to calculate proton diffusion coefficient. Selected materials were tested as electrolytes in solid oxide fuel cells.

Strontium-substituted Ba(Ce,Zr)O3-δ oxides for proton conducting membranes

This paper is focused on Ba1-xSrx(Ce0.75Zr0.25)0.9Nd0.1O2.95 proton-conducting oxides, for which the effect of substitution of barium by strontium in a full range of compositions is studied. Crystal lattice symmetry, proton conductivity and stability in CO2 atmosphere are discussed. Substitution of barium by strontium reduces toxicity and does not deteriorate chemical stability, however, crystal lattice of the strontium-substituted perovskites is more distorted, causing reduction of proton conductivity more than one order of magnitude. Balance between opposite tendencies can be found at low Sr content, e.g., 25 at.%.