Elucidating the Lithiation Process in Fe_3-O₄ Nanoparticles by Correlating Magnetic and Structural Properties

Due to their high potential energy storage, magnetite (Fe3O4) nanoparticles have become appealing as anode materials in lithium-ion batteries. However, the details of the lithiation process are still not completely understood. Here, we investigate chemical lithiation in 70 nm cubic-shaped magnetite nanoparticles with varying degrees of lithiation, x = 0, 0.5, 1, and 1.5. The induced changes in the structural and magnetic properties were investigated using X-ray techniques along with electron microscopy and magnetic measurements. The results indicate that a structural transformation from spinel to rock salt phase occurs above a critical limit for the lithium concentration (x(c)), which is determined to be between 0.5< x(c) <= 1 for Fe3-delta O4. Diffraction and magnetization measurements clearly show the formation of the antiferromagnetic LiFeO2 phase. Upon lithiation, magnetization measurements reveal an exchange bias in the hysteresis loops with an asymmetry, which can be attributed to the formation of mosaic-like LiFeO2 subdomains. The combined characterization techniques enabled us to unambiguously identify the phases and their distributions involved in the lithiation process. Correlating magnetic and structural properties opens the path to increasing the understanding of the processes involved in a variety of nonmagnetic applications of magnetic materials.