Quantitative Determination of the Compositional Inhomogeneity in NMC Cathode Materials by Williamson-Hall Analysis
Authors: Tahmasebi Mohammad Hossein , Obrovac Mark 
Published: February 2024

Over the past decades, the co-precipitation synthesis technique has been used, particularly for making LiNixMnyCozO2 (NMC) cathode materials for lithium-ion batteries (LIBs), due to better control of particle morphology and higher compositional homogeneity in the final NMC product compared to other methods. However, the co-precipitation method introduces complexity and consumes large amounts of energy and water, which can increase cost. This has led researchers to investigate solid-state NMC synthesis techniques in order to improve sustainability and reduce LIB cost [1-3]. Obtaining homogeneous mixing of transition metals at the atomic scale by solid-state methods remains a challenge. Since compositional homogeneity has a vital effect on the electrochemical performance of the NMCs, it is essential to quantitatively estimate the degree of inhomogeneity in cathode materials for the development of new synthesis methods.
In the present study, a quantitative X-ray diffraction (XRD) analysis technique using the Williamson-Hall (WH) method is used to determine the degree of inhomogeneity in NMC precursors and NMC cathode materials. In this regard, single-phase rock salt (RS) precursors with varying degrees of transition metal homogeneity were prepared by combining NiO, MnO and CoO by grinding for different times, followed by heating under an Ar flow. Then, NMC cathode materials were made by heating the RS-precursors with lithium carbonate in air. EDS elemental maps showed that transition metal inhomogeneity existed in the RS-precursors and final NMCs and that this inhomogeneity is primarily associated with the Mn distribution (Figure 1(a)). Furthermore, the compositional inhomogeneity became reduced with increasing precursor grinding time.
Using a WH analysis method, composition variation in the NMC precursor and in the final NMC product could be quantitatively determined from conventional XRD powder patterns. Utilizing this analysis, it was found that inhomogeneity in the precursor is translated into the final NMC, so that a similar trend in the degree of inhomogeneity was observed for both synthesized precursors and their NMC products (Figure 1(b) and (c)). Additionally, NMCs with high compositional homogeneity showed much better electrochemical performance compared to the samples with higher degree of inhomogeneity. We believe the proposed method is highly useful in the development of new cathode precursors and in predicting the performance of the NMC cathode materials by quantitatively determining their degree of compositional inhomogeneity.

References

1. M. N. Obrovac, L. Zheng, and M. D. L. Garayt, Engineered Particle Synthesis by Dry Particle Microgranulation, Cell Reports Physical Science, 1, 100063 (2020).
2. L. Zheng, J. C. Bennett, and M. N. Obrovac, All-Dry Synthesis of Single Crystal NMC Cathode Materials for Li-Ion Batteries, J. Electrochem. Soc., 167, 130536 (2020).
3. M. H. Tahmasebi, L. Zheng, T. D. Hatchard, M. N. Obrovac, Li[Ni0.6Mn0.2Co0.2]O2 Made From Crystalline Rock Salt Oxide Precursors, J. Electrochem. Soc., 170, 030531 (2023).

Figure 1