A study on Ti-doped Fe₃O₄ anode for Li ion battery using machine learning, electrochemical and distribution function...

Among many transition-metal oxides, Fe₃O₄ anode based lithium ion batteries (LIBs) have been well-investigated because of their high energy and high capacity. Iron is known for elemental abundance and is relatively environmentally friendly as well contains with low toxicity. However, LIBs based on Fe₃O₄ suffer from particle aggregation during charge-discharge processes that affects the cycling performance. This study conjectures that iron agglomeration and material performance could be affected by dopant choice, and improvements are sought with Fe₃O₄ nanoparticles doped with 0.2% Ti. The electrochemical measurements show a stable specific capacity of 450 mAh g^-1 at 0.1 C rate for at least 100 cycles in Ti doped Fe₃O₄. The stability in discharge capacity for Ti doped Fe₃O₄ is achieved, arising from good electronic conductivity and stability in microstructure and crystal structure, which has been further confirmed by density functional theory (DFT) calculation. Detailed distribution function of relaxation times (DFRTs) analyses based on the impedance spectra reveal two different types of Li ion transport phenomena, which are closely related with the electron density difference near the two Fe-sites. Detailed analyses on EIS measurements using DFRTs for Ti doped Fe₃O₄ indicate that improvement in interfacial charge transfer processes between electrode and Li metal along with an intermediate lithiated phase helps to enhance the electrochemical performance.