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  • Open Access

Short-range charge ordering in Mn-doped LiFePO4

Souzan Hammadi, Fabian Schwarz, Jolla Kullgren, Daniel Brandell, and Peter Broqvist

  • Department of Chemistry – Ångström Laboratory, Uppsala University, 75121 Uppsala, Sweden

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Phys. Rev. B 112, 184109 – Published 14 November, 2025

DOI: https://doi.org/10.1103/wzsf-5cln

Abstract

This paper explores the impact of Mn doping in the battery electrode material Li(Mn)FePO4 by computational methods. Structures are generated at up to 6.25% Li and 3.125% Mn content with varying Li, Fe, and Mn configurations. The oxidation state of the Fe and Mn ions are explicitly set using occupation matrix control, while the structures are optimized using DFT+U. Although Mn is redox active and can exist in both the +III and +II states, there is a strong preference for the latter. We show that the charge-compensating electrons prefer to occupy the Mn sites rather than the Fe sites during Li insertion. This results in Mn(II) and Fe(II) ions that interact electrostatically with the positively charged Li ions. The DFT+U data are consequently used to parametrize a Coulomb potential, incorporating short-range two-body corrections, and utilized within a Monte Carlo approach. The short-range order between the atomic species are then quantified by their coordination numbers at varying temperatures. The Monte Carlo sampling demonstrates lower Li-Li clustering in the Li(Mn)FePO4 system at temperatures below 500 K and thus more disorder as compared to the undoped system. On average, this results in less cluster formation, which correlates with the enlarged solid solution region found in the LiMnFePO4 phase diagram.

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References (52)

  1. Z. Li, D. Liu, J. Xiong, L. He, Z. Zhao, and D. Wang, Selective recovery of lithium and iron phosphate/carbon from spent lithium iron phosphate cathode material by anionic membrane slurry electrolysis, Waste Manage. (Oxford) 107, 1 (2020).
  2. N. Nitta, F. Wu, J. T. Lee, and G. Yushin, Li-ion battery materials: Present and future, Mater. Today 18, 252 (2015).
  3. S. Evro, A. Ajumobi, D. Mayon, and O. S. Tomomewo, Navigating battery choices: A comparative study of lithium iron phosphate and nickel manganese cobalt battery technologies, Future Batteries 4, 100007 (2024).
  4. L.-X. Yuan, Z.-H. Wang, W.-X. Zhang, X.-L. Hu, J.-T. Chen, Y.-H. Huang, and J. B. Goodenough, Development and challenges of LiFePO4 cathode material for lithium-ion batteries, Energy Environ. Sci. 4, 269 (2011).
  5. A. K. Padhi, K. S. Nanjundaswamy, and J. B. Goodenough, Phospho‐olivines as positive‐electrode materials for rechargeable lithium batteries, J. Electrochem. Soc. 144, 1188 (1997).
  6. S. Kaushik, T. Mehta, P. Chand, S. Sharma, and G. Kumar, Recent advancements in cathode materials for high-performance Li-ion batteries: Progress and prospects, J. Energy Storage 97, 112818 (2024).
  7. N. Ohmer, B. Fenk, D. Samuelis, C.-C. Chen, J. Maier, M. Weigand, E. Goering, and G. Schütz, Phase evolution in single-crystalline LiFePO4 followed by in situ scanning X-ray microscopy of a micrometre-sized battery, Nat. Commun. 6, 6045 (2015).
  8. G. Chen, X. Song, and T. J. Richardson, Electron microscopy study of the LiFePO4 to FePO4 phase transition, Electrochem. Solid-State Lett. 9, A295 (2006).
  9. C. Delacourt, P. Poizot, J.-M. Tarascon, and C. Masquelier, The existence of a temperature-driven solid solution in LixFePO4 for 0 ≤ x ≤ 1, Nat. Mater. 4, 254 (2005).
  10. J. L. Dodd, R. Yazami, and B. Fultz, Phase diagram of LixFePO4, Electrochem. Solid-State Lett. 9, A151 (2006).
  11. H. Liu, F. C. Strobridge, O. J. Borkiewicz, K. M. Wiaderek, K. W. Chapman, P. J. Chupas, and C. P. Grey, Capturing metastable structures during high-rate cycling of LiFePO4 nanoparticle electrodes, Science 344, 1252817 (2014).
  12. P. Bai, D. A. Cogswell, and M. Z. Bazant, Suppression of phase separation in LiFePO4 Nanoparticles during battery discharge, Nano Lett. 11, 4890 (2011).
  13. T. Nakamura, K. Sakumoto, S. Seki, Y. Kobayashi, M. Tabuchi, and Y. Yamada, Apparent diffusion constant and electrochemical reaction in LiFe1xMnxPO4 olivine cathodes, J. Electrochem. Soc. 154, A1118 (2007).
  14. C. Li, N. Hua, C. Wang, X. Kang, T. Wumair, and Y. Han, Effect of Mn2+-doping in LiFePO4 and the low temperature electrochemical performances, J. Alloys Compd. 509, 1897 (2011).
  15. Y. Liu, Y. J. Gu, J. L. Deng, G. Y. Luo, F. Z. Wu, Y. Mai, X. Y. Dai, and J. Q. Li, Effect of doped Mn on improving the electrochemical performance of LiFePO4, J. Mater. Sci.: Mater. Electron. 31, 2887 (2020).
  16. Y. Wang, Z. S. Feng, L. L. Wang, L. Yu, J. J. Chen, Z. Liang, and R. Wang, A joint experimental and theoretical study on the effect of manganese doping on the structural, electrochemical and physical properties of lithium iron phosphate, RSC Adv. 4, 51609 (2014).
  17. C. U. Mulik, R. S. Kamat, X. Wang, C. Padwal, M. Y. Chougale, D. P. Dubal, and L. D. Jadhav, High-performance Li-ion battery cathode: Mn-doped LiFePO4 via solution combustion synthesis method, J. Electroanal. Chem. 971, 118568 (2024).
  18. D. B. Ravnsbæk, K. Xiang, W. Xing, O. J. Borkiewicz, K. M. Wiaderek, P. Gionet, K. W. Chapman, P. J. Chupas, and Y. M. Chiang, Extended solid solutions and coherent transformations in nanoscale olivine cathodes, Nano Lett. 14, 1484 (2014).
  19. T. Nakamura, Y. Miwa, M. Tabuchi, and Y. Yamada, Structural and surface modifications of LiFePO4 olivine particles and their electrochemical properties, J. Electrochem. Soc. 153, A1108 (2006).
  20. K. T. Lee and K. S. Lee, Electrochemical properties of LiFe0.9Mn0.1PO4/Fe2P cathode material by mechanical alloying, J. Power Sources 189, 435 (2009).
  21. R. Malik, F. Zhou, and G. Ceder, Phase diagram and electrochemical properties of mixed olivines from first-principles calculations, Phys. Rev. B 79, 214201 (2009).
  22. B. Ellis, L. K. Perry, D. H. Ryan, and L. F. Nazar, Small polaron hopping in LixFePO4 solid solutions: Coupled lithium-ion and electron mobility, J. Am. Chem. Soc. 128, 11416 (2006).
  23. K. Zaghib, A. Mauger, J. B. Goodenough, F. Gendron, and C. M. Julien, Electronic, optical, and magnetic properties of LiFePO4: Small magnetic polaron effects, Chem. Mater. 19, 3740 (2007).
  24. F. Zhou, T. Maxisch, and G. Ceder, Configurational electronic entropy and the phase diagram of mixed-valence oxides: The case of LixFePO4, Phys. Rev. Lett. 97, 155704 (2006).
  25. S. Hammadi, J. Kullgren, M. J. Wolf, D. Brandell, and P. Broqvist, Impact of temperature on short-range charge ordering in LiFePO4/FePO4, Phys. Rev. B 109, 144103 (2024).
  26. G. Kresse and D. Joubert, From ultrasoft pseudopotentials to the projector augmented-wave method, Phys. Rev. B 59, 1758 (1999).
  27. J. P. Perdew, K. Burke, and M. Ernzerhof, Generalized gradient approximation made simple, Phys. Rev. Lett. 77, 3865 (1996).
  28. S. L. Dudarev, G. A. Botton, S. Y. Savrasov, C. J. Humphreys, and A. P. Sutton, Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study, Phys. Rev. B 57, 1505 (1998).
  29. A. Jain, G. Hautier, S. P. Ong, C. J. Moore, C. C. Fischer, K. A. Persson, and G. Ceder, Formation enthalpies by mixing GGA and GGA+U calculations, Phys. Rev. B 84, 045115 (2011).
  30. J. P. Allen and G. W. Watson, Occupation matrix control of d- and f-electron localisations using DFT+U, Phys. Chem. Chem. Phys. 16, 21016 (2014).
  31. A. K. Akshay, E. Wadbro, C. Köhler, P. Mitev, P. Broqvist, and J. Kullgren, CCS: A software framework to generate two-body potentials using curvature constrained splines, Comput. Phys. Commun. 258, 107602 (2021).
  32. J. D. Gale and A. L. Rohl, The general utility lattice program (GULP), Mol. Simul. 29, 291 (2003).
  33. A. T. Phan, A. E. Gheribi, and P. Chartrand, Coherent and para-equilibrium phase transformations in Mn-doped-LiFePO4 cathode materials: Implications for lithium ion battery performances, J. Alloys Compd. 838, 155550 (2020).
  34. Y.-S. Yu, M. Farmand, C. Kim, Y. Liu, C. P. Grey, F. C. Strobridge, T. Tyliszczak, R. Celestre, P. Denes, J. Joseph, H. Krishnan, F. R. N. C. Maia, A. L. D. Kilcoyne, S. Marchesini, T. P. C. Leite, T. Warwick, H. Padmore, J. Cabana, and D. A. Shapiro, Three-dimensional localization of nanoscale battery reactions using soft X-ray tomography, Nat. Commun. 9, 921 (2018).
  35. B. M. May, Y.-S. Yu, M. V. Holt, F. C. Strobridge, U. Boesenberg, C. P. Grey, and J. Cabana, Nanoscale detection of intermediate solid solutions in equilibrated LixFePO4 microcrystals, Nano Lett. 17, 7364 (2017).
  36. S. Hammadi, Souzanha/SRO_Mn_doping_LiFePO4: Short range charge ordering in Mn-doped LiFePO4, Zenodo (2025), https://doi.org/10.5281/zenodo.17478933.
  37. H. Yaghoobnejad Asl and A. Manthiram, Proton-induced disproportionation of Jahn-Teller-active transition-metal ions in oxides due to electronically driven lattice instability, J. Am. Chem. Soc. 142, 21122 (2020).
  38. A. Yamada, Y. Takei, H. Koizumi, N. Sonoyama, R. Kanno, K. Itoh, M. Yonemura, and T. Kamiyama, Electrochemical, magnetic, and structural investigation of the Lix(MnyFe1−y)PO4 olivine phases, Chem. Mater. 18, 804 (2006).
  39. Z. Nie, C. Ouyang, J. Chen, Z. Zhong, Y. Du, D. Liu, S. Shi, and M. Lei, First principles study of Jahn–Teller effects in LixMnPO4, Solid State Commun. 150, 40 (2010).
  40. S. Zhang, Z. Yang, Y. Lu, W. Xie, Z. Yan, and J. Chen, Insights into cation migration and intermixing in advanced cathode materials for lithium‐ion batteries, Adv. Energy Mater. 14, 2402068 (2024).
  41. A. Renuka Balakrishna, Y.-M. Chiang, and W. C. Carter, Phase-field model for diffusion-induced grain boundary migration: An application to battery electrodes, Phys. Rev. Mater. 3, 065404 (2019).
  42. G. Bree, J. Zhao, V. Majherova, D. Proprentner, G. J. Paez Fajardo, and L. F. J. Piper, Practical pathways to higher energy density LMFP battery cathodes, Sustainable Energy Fuels 39, 3683 (2025).
  43. F. Jiang, K. Qu, M. Wang, J. Chen, Y. Liu, H. Xu, Y. Huang, J. Li, P. Gao, J. Zheng, M. Chen, and X. Li, Atomic scale insight into the fundamental mechanism of mn doped LiFePO4, Sustainable Energy Fuels 4, 2741 (2020).
  44. E. E. Nazarov, A. D. Dembitskiy, I. A. Trussov, O. A. Tyablikov, I. S. Glazkova, S. V. Alexey, I. A. Presniakov, I. V. Mikheev, A. V. Morozov, V. A. Nikitina, A. M. Abakumov, E. V. Antipov, and S. S. Fedotov, A Li-rich strategy towards advanced Mn-doped triphylite cathodes for Li-ion batteries, Energy Advances 2, 328 (2023).
  45. S. Yaroslavtsev and S. C. Müller, Detection of metastable solid solution in doped LiFePO4 by synchrotron nuclear resonance techniques, Mater. Today Chem. 39, 102159 (2024).
  46. P. Vanaphuti and A. Manthiram, Enhancing the mn redox kinetics of LiMn0.5Fe0.5PO4 cathodes through a synergistic co‐doping with Niobium and Magnesium for lithium‐ion batteries, Small 20, 2404878 (2024).
  47. Y. Cao, J. He, W. Tu, R. Li, W. Luo, X. Zhang, J. Duan, D. Wang, X. Wang, P. Dong, and Y. Zhang, Beneficial effect of incorporating particle nanocrystalline and V3+ doping into high-energy-density LiMn0.8Fe0.2PO4 for lithium-ion batteries, Solid State Ionics 411, 116576 (2024).
  48. P. Liu, Y.-L. Cao, Z. Chen, and Y.-L. Xie, Enhancement of cathode superior kinetics and Li-storage properties of LiMn0.5Fe0.5PO4@C cathode materials by Ni doping strategy, Electrochim. Acta 524, 145991 (2025).
  49. Y. Xiao, F. C. Zhang, and J. I. Han, Synthesis, characterization and lithium-ion migration dynamics simulation of LiFe1xTxPO4 (T=Mn, Co, La and Ce) doping cathode material for lithium-ion batteries, Appl. Phys. A 122, 980 (2016).
  50. M. B. Sahana, S. Vasu, N. Sasikala, S. Anandan, H. Sepehri-Amin, C. Sudakar, and R. Gopalan, Raman spectral signature of Mn-rich nanoscale phase segregations in carbon free LiFe1xMnxPO4 prepared by hydrothermal technique, RSC Adv. 4, 64429 (2014).
  51. Y. Lin, Y. Lin, B. Zeng, G. Zhao, T. Zhou, M. Chen, X. Mao, H. Lai, and Z. Huang, An optimized Mn-doped LiFePO4/C composite synthesized by carbonthermal reduction technique, Int. J. Electrochem. Sci. 6, 6653 (2011).
  52. M. Togo and A. Nakahira, Structure refinement of Mn-substituted LiMnxFe1−xPO4, Mater. Sci. Appl. 09, 542 (2018).

Outline

Information

Phys. Rev. B 112, 184109– Published 14 November, 2025
  • Received 27 August 2025
  • Revised 29 October 2025
  • Accepted 3 November 2025
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