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Advances in neutron diffraction for structural characterization of lithium orthophosphates LiMPO4

Polina E. Romashko, Mikhail A. Semkin, Elena A. Filonova, Aleksander N. Pirogov

Abstract


Olivine-type lithium orthophosphates LiMPO4 (M=Fe, Mn, Co, Ni) are one of the most important families of polyanion cathode materials for lithium-ion batteries owing to their excellent thermal and chemical stability, low cost, and high safety. While LiFePO4 has achieved commercial success, mixed compositions such as LiFe1–xMnₓPO4 and LiNi1–xCoxPO4 are actively studied to increase energy density while retaining the stability of the olivine framework. Despite extensive research, several key challenges remain, including accurate lithium localization, quantitative determination of Li/M anti-site defects, identification of Li+ diffusion pathways, and refinement of magnetic structures. Many of these issues cannot be fully resolved using conventional X-ray diffraction alone. Neutron diffraction has become an indispensable tool for addressing these issues owing to its high sensitivity to light elements, ability to distinguish neighboring 3d-transition metals, and unique interaction with magnetic moments. This review summarizes recent advances in neutron diffraction studies of LiMPO4, including crystal and magnetic structures, defect chemistry, and operando investigations. The capabilities of neutron diffraction are compared with complementary techniques. The results demonstrate that neutron diffraction continues to provide critical atomic-level insights essential for the design of next-generation olivine cathodes.

Keywords


lithium-ion batteries; olivine phosphates; neutron diffraction; crystal structure; magnetic structure; anti-site defects; operando studies

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References


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DOI: https://doi.org/10.15826/chimtech.10370

Copyright (c) 2026 Polina E. Romashko, Mikhail A. Semkin, Elena A. Filonova, Aleksander N. Pirogov

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