Hydrothermal crystallization of Pmn21 Li2FeSiO4 hollow mesocrystals for Li-ion cathode application

Abstract Lithium transition metal orthosilicates such as Li 2 FeSiO 4 (LFS) have been recognized as promising cathode materials for application in Li-ion batteries because of their high theoretical energy density, safety, and benign/abundant element composition. Their development, however, has been hampered by the challenge of obtaining phase-pure and defect-free Li 2 FeSiO 4 nanoparticles as non-optimized crystal properties have an adverse effect on structural stability and electrochemical performance. Considering the sustainable potential of hydrothermal synthesis in producing electrode materials, here we employ this process to systematically study critical synthesis parameters for optimal control of particle size, morphology, phase purity, and defects of Li 2 FeSiO 4 crystallized in the orthorhombic crystal system with space group Pmn 2 1 . It is shown that via a combination of elevated FeSO 4 concentration regime and use of EDTA as a complexing agent, phase-pure Pmn 2 1 particle formation can be controlled. Synchrotron-based XRD Rietveld refinement and 57 Fe Mossbauer spectroscopy reveal a significant reduction in Li-Fe antisite defects and presence of Fe 3+ . Additionally, the use of EDTA promotes the formation of unique peanut-shell looking hollow mesocrystals that are advantageous in maximizing electrode/electrolyte contact resulting in higher Li-ion storage capacity than dense LFS particles. On the basis of detailed XRD, SEM, and TEM characterizations, a four-step crystallization mechanism is proposed to explain the formation of the hollow mesocrystals. These findings bring new insight into our pursuit of optimization of Li 2 FeSiO 4 as a cathode material for Li-ion batteries.