Effect of Mn, N co-doped LiFePO4 on electrochemical and mechanical properties: A DFT study

• Published in: Journal of molecular graphics & modelling Vol. 125; p. 108604
• Main Authors: Wang, Shucheng, Wang, Fazhan
• Format: Journal Article
• Language: English
• Published: Elsevier Inc 01-12-2023
• Subjects: Electrochemical properties; First-principles; LiFePO4 battery; Mechanical properties; N doping; Mechanical properties; Mn; LiFePO4 battery; Electrochemical properties; First-principles; N doping
• ISSN: 1093-3263; 1873-4243
• DOI: 10.1016/j.jmgm.2023.108604

In this study, the thermodynamic stability, embedding voltage, volume change rate, electronic structure properties, mechanical properties and lithium-ion diffusion characteristics of the Mn, N co-doped LiFePO4 material are investigated using a first-principles approach based on density generalization theory. The results show that the doped system has a low formation energy and the material meets the thermodynamic stability criteria. During the de-lithium process, the volume change rate of the doped material decreases and the cycling performance is improved, but the battery energy density decreases slightly. It is also found that the doping of N led to the transformation of the material from a p-type semiconductor to an N-type semiconductor, while the doping of Mn and N lead to the creation of impurity bands, narrowing of the band gap and an increase in conductivity. At the same time, Mn, N co-doping greatly improve the ductility of the material, suppress the generation of microcracks, and reduce the possibility of shear deformation. In addition, it is noteworthy that the lithium-ion diffusion energy barrier of the doped system is reduced, which predicts an increase in the diffusion rate of lithium ions in the doped system.
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•The modification of manganese and nitrogen co-doped LiFePO4 materials has been investigated for the first time using a first-principles approach.•The thermodynamic stability, intercalation voltage, volume change rate, electronic structure properties, mechanical properties and lithium-ion diffusion properties of LiFePO4 crystal structure before and after doping were analyzed.