A Study of the Thermodynamics and Kinetics of LiₓFePO₄ as a Cathode Material for Li Batteries

Abstract

Olivine-type LiFePO4 has been recognized as one of the most promising cathode materials for rechargeable Li batteries. Its advantages include high capacity, high stability, nontoxicity, and low cost. Our methods for synthesizing nanocrystalline LixFePO4 with the olivine structure are described. Solid-state reactions and precipitation reactions were both successful, and ball milling was especially effective at reducing crystallite sizes. Diffractometry and microscopy were used to characterize these materials, and results of impurity phases, excess Fe3+, and internal stresses are reported for the different types of synthesis. Applications of lithium-ion batteries, including automotive applications, require fast kinetics and high conductivity of ions and electrons. Unfortunately, LixFePO4 has the electronic structure of an insulator, an entirely unsatisfactory situation if it is to be used as a battery electrode. Electrical conductivity in LixFePO4 occurs by the motion of small polarons, which are valence electrons at Fe atoms plus their distorted local environments. Electrical conductivity of LixFePO4 is interpreted in terms of small polaron hopping. There are other factors of importance in these measurements, such as impurities or defects that block the one-dimensional conduction channels of the olivine structure of LixFePO4. We studied the polaron hopping directly, which allows us to understand the intrinsic electrical conductivity, and how it depends on microstructure and composition of LixFePO4. The experimental technique was Mossbauer spectrometry, which has been used for many years as a means for determining the fractions of Fe2+ and Fe3+ in a material. Usually the spectral signatures of Fe2+ and Fe3+ are distinct. When valence electrons hop between Fe2+ and Fe3+ at a frequency of 108 Hz or higher, however, the valence changes during the timescale of the Mossbauer measurement and the spectrum is blurred. By measuring Mossbauer spectra at elevated temperatures, we can determine the fractions of Fe atoms participating in polaron hopping, and determine the activation energy of the process. From this we estimate intrinsic electrical conductivities of 10-7S/cm at room temperature for nanocrystalline Li0.5FePO4, for example. We find a comparable conductivity for LixFePO4 prepared as a solid solution, but the conductivity of conventional LixFePO4 is much lower. There has been much discussion about how surface area might thermodynamically stabilize the solid solution phase of nanocrystalline LixFePO4. In a series of X-ray diffraction measurements, some at elevated temperatures, we found the solid solution phase of LixFePO4 to be especially robust at room temperature when the material was prepared in nanocrystalline form. Moreover, the consistent phase transition temperature around 200°C was observed, as evidence for the unchanged equilibrium phase diagram by crystallite size. This is consistent with our evaluation on the boundaries of the two-phase mixture of triphylite and heterosite during Li insertion and extraction. Profiles of entropy and enthalpy changes were evaluated by open-circuit voltage measurements. The boundaries were found at x=0.05 and 0.95 in the LixFePO4 with crystal size of 70 nm, similar to the reported values on bulk-LixFePO4. These are important in practice, because electrochemical lithiation and delithiation at room temperature should remain as a two-phase transformation, even if a solid solution of lithium is present in the initial electrode material.