In-depth approach and establishment from a structural perspective of LiFePO4 cathodes for lithium-ion batteries by a two-step sintering

Most synthesis of olivine LiFePO4 (LFP) studies have emphasized the importance of a two-step sintering process for the formation of a uniform carbon coating. However, in this study, it is found that, as an advantage of the two-step sintering process, stable carbonization not only improves lithium-ion conductivity by forming a coating layer but also increases the uniformity of the internal crystal structure. In addition to basic crystallinity and structure analysis using X-ray diffraction (XRD), in-depth calculations are performed to explain the formation mechanism of crystal structure according to the two-step sintering process and the temperature of the first sintering step. In particular, lattice defects and structural uniformity are closely investigated from the crystal structure perspective by comparing lattice micro-strain and dislocation density. Improvement in lithium-ion conductivity from structural uniformity is also demonstrated through cyclic voltammetry (CV) analysis. As a result, it is confirmed that LFP, which undergoes a high-temperature two-step sintering, has high capacity and excellent cycle retention at high rates. Furthermore, ex-situ XRD analysis demonstrates the performance difference according to lithium-ion mobility by comparing the LiFePO4/FePO4 two-phase transformation reaction of two-step sintered LFP and the plateau stability during charging. [Display omitted] •A 2-step sintering of LFP including HT-1st-step showed high structural uniformity.•Stable carbonization from HT-1st-step sintering increased lithium-ion conductivity.•In-depth structural analysis of LFP was established through XRD coupling equation.•Structural uniformity is emphasized through LFP/FP transition and plateau property.