Issues $\rightarrow$ Volume 27, Issue 3 (2026)

Effects of Transition Metals (Ti, Co, Ni and Mn) on the Electrochemical Performance of Cathode Composite Materials: Synthesis and Characterisation of xLi2TiO3, yLiCoO2, and (1−x−y)LiNi1/2Mn1/2O2 Ternary Composites

MONAJJEMI M. and MOLLAAMIN F.

Kastamonu University, 37150 Kastamonu, Turkey

Received / final version: 31.01.2026 / 20.07.2026 Download PDF logo PDF

Abstract
Progress in the physics of metals has shown that their electronic structure governs both metallic conductivity and the tendency of metals to form oxides. Modern theories, such as band theory, explain that metallic conductivity arises from delocalized electrons in partially filled energy bands. Metals, which readily lose electrons, tend to form stable oxides, whereas metals, which hold their electrons more strongly, show lower reactivity toward oxygen. Consequently, metals with high electrical conductivity generally have a lower tendency to form stable oxides. However, further progress in the metal and oxide physics revealed that some metals, such as aluminium and titanium, form thin, stable, insulating oxide layers. Based on these approaches, we synthesised a ternary composite of several transition-metal oxides for lithium-ion batteries. Although lithium transition-metal oxides are high-capacity electrochemically active materials, their structural instability at high voltages (e.g., > 4.3 V) detrimentally affects battery performance. To address this issue, we propose a ternary composite material capable of forming a medium-entropy structural phase with partial cation disorder after initial delithiation. The objective of this work is to synthesise a composite compound with lower cost and higher cyclability than commercially available lithium-ion battery cathode materials. A ternary design of transition-metal oxide composites containing Li2TiO3 and LiNi1/2Mn1/2O2 is employed instead of using LiCoO2 alone, thereby, reducing the cobalt content in the cathode material. As a result, the synthesised compound offers reduced cost and toxicity associated with cobalt, contributing to a cleaner and safer environment. Ten samples were prepared using xLi2TiO3, yLiCoO2, and (1−x−y)LiNi1/2Mn1/2O2 compositions. As found through the Raman spectroscopy, x-ray diffraction, and electrochemical analysis, the LiNi1/6Mn1/6Ti1/3Co1/3O2 composite exhibits superior electrochemical performance, including higher initial charge and discharge capacities and improved cyclability, compared with traditional cathode materials.

Keywords: lithium-ion batteries (Li-ion batteries), cathode materials, Li2TiO3, LiCoO2, LiNi1/2Mn1/2O2, ternary composites.

DOI: https://doi.org/10.15407/ufm.27.03.395

Citation: M. Monajjemi and F. Mollaamin, Effects of Transition Metals (Ti, Co, Ni and Mn) on the Electrochemical Performance of Cathode Composite Materials: Synthesis and Characterisation of xLi2TiO3, yLiCoO2, and (1−x−y)LiNi1/2Mn1/2O2 Ternary Composites, Progress in Physics of Metals, 27, No. 3: 395–*** (2026)

References  
  1. Y. Makimura and T. Ohzuku, J. Power Sources, 119–121: 156–160 (2003); https://doi.org/10.1016/S0378-7753(03)00170-8
  2. L. Zhang, K. Takada, N. Ohta, K. Fukuda, and T. Sasaki, J. Power Sources, 146, Nos. 1–2: 598–601 (2005); https://doi.org/10.1016/j.jpowsour.2005.03.122
  3. S. Gopukumar, K.Y. Chung, and K.B. Kim, Electrochim. Acta, 49, No. 5: 803–810 (2004); https://doi.org/10.1016/j.electacta.2003.09.034
  4. Y.K. Sun, Y. Bae, and S.T. Myung, J. Appl. Electrochem., 35: 151–156 (2005); https://doi.org/10.1007/s10800-004-6197-5
  5. T. Ohzuku and Y. Makimura, Chem Lett, 30, No. 8: 744–745 (2002); https://doi.org/10.1246/cl.2001.744
  6. Y. Makimura and T. Ohzuku, J. Power Sources, 119–121: 156–160 (2003); https://doi.org/10.1016/S0378-7753(03)00170-8
  7. M. Monajjemi, F. Mollaamin, S. Shahriari, Z. Khalaj, H. Sakhaeinia, and A. Alihosseini, Russ. J. Phys. Chem. B, 18, No. 4: 1090–1112 (2024); https://doi.org/10.1134/S1990793124700465
  8. M. Monajjemi, S. Mohammadi, S. Shahriari, and F. Mollaamin, Russ. J. Phys. Chem. B, 18, No.1: 308–324 (2024); https://doi.org/10.1134/S1990793124010342
  9. X. Xiang and W. Li, Electrochim. Acta, 127: 259–265(2014); https://doi.org/10.1016/j.electacta.2014.02.037
  10. R. Yu, Y. Lin, and Z. Huang, Electrochim. Acta, 173, No. 10: 515–522 (2015); https://doi.org/10.1016/j.electacta.2015.05.084
  11. Y. Liu, O. Wang, Y. Lu, B. Yang, M. Su, Y. Gao, and A. Dou, J. Alloys Compd., 638, No. 25: 1–6 (2015).
  12. E. Zhao, X. Liu, Z. Hu, L. Sun, and X. Xiao, J. Power Sour, 294, No. 30: 141–149 (2015); https://doi.org/10.1016/j.jpowsour.2015.06.059
  13. D. Xiang, L.N. Xiao, Y. Li, Z.F. Tang, J.W. Wan, Z.Y. Wen, and C.H. Chen, J. Power Sources, 390, No. 30: 13–19 (2018); https://doi.org/10.1016/j.jpowsour.2018.04.034
  14. K. Yang, L.Z. Fan, J. Guo, and X. Qu, Electrochim. Acta, 63, No. 29: 363–368 (2012); https://doi.org/10.1016/j.electacta.2011.12.121
  15. B. Ramasubramanian, S. Sundarrajan, V. Chellappan, M.V. Reddy, S. Ramakrishna, and K. Zaghib, Batteries, 8, No. 10: 133 (2022); https://doi.org/10.3390/batteries8100133
  16. J. Tian, R.Xiong, W. Shen, and J. Lu, Appl. Energy, 291: 116812 (2021); https://doi.org/10.1016/j.apenergy.2021.116812
  17. J. Kumar, R.R. Neiber, J. Park, R.A. Soomro, G.W. Greene, S.A. Mazari, H.Y. Seo, J.H. Lee, M. Shon, and D.W. Chang, Chem. Eng. J., 431: 133993 (2022); https://doi.org/10.1016/j.cej.2021.133993
  18. H.-D. Yang, Y.-Y. Kang, P.-P. Zhu, Q.-W. Chen, L. Yang, and J.-P. Zhou, J. Alloys Compd., 872: 159759 (2021); https://doi.org/10.1016/j.jallcom.2021.159759
  19. M. Koudriachova, Chem. Phys. Lett., 458: 108–112 (2008); https://doi.org/10.1016/j.cplett.2008.04.024
  20. W. Mackrodt, J. Solid State Chem., 142, No. 2: 428–439 (1999); https://doi.org/10.1006/jssc.1998.8058
  21. D.I. Shlimas, A.L. Kozlovskiy, and M.V. Zdorovets, J. Mater. Sci. Mater. Electron., 32, No. 9: 7410–7422 (2021); https://doi.org/10.1007/s10854-021-05454-z
  22. K. Jiang, X. Hu, H. Sun, D. Wang, X. Jin, and Y. Ren, Chem. Mater., 16, No. 22: 4324–4329 (2004); https://doi.org/10.1021/cm0494148
  23. D.R. Zhang, H.L. Liu, R.H. Jin, N.Z. Zhang, Y.X. Liu, and Y.S. Kang, J. Ind. Eng. Chem., 13, No. 1: 92–96 (2007).
  24. L.H. Yang, C. Dong, and J. Guo, J. Power Sources, 175, No. 1: 575–580 (2008); https://doi.org/10.1016/j.jpowsour.2007.09.002
  25. C. Julien, L. El-Farh, S. Rangan, and M. Massot, J. Sol-Gel Sci. Technol., 15, No. 1: 63–72 (1999); https://doi.org/10.1023/A:1008765030990
  26. Y.-S. Lee, Y.-K. Sun, and K.-S. Nahm, Solid State Ionics, 109, Nos. 3–4: 285–294 (1998); https://doi.org/10.1016/S0167-2738(98)00085-X
  27. B.E. Yoldas, J. Sol–Gel Sci. Technol., 1: 65–77 (1993).
  28. L. Li, H. Yu, and Y. Chen, Atmosphere, 13: 1959 (2022); https://doi.org/10.3390/atmos 13121959
  29. F. Izumi and K. Momma, Solid State Phenom., 130: 15–20 (2007); https://doi.org/10.4028/www.scientific.net/SSP.130.15
  30. M. Monajjemi, Struct. Chem., 23: 551–580 (2012); https://doi.org/10.1007/s11224-011-9895-8
  31. M. Monajjemi, S. Ketabi, and A. Amiri, Russ. J. Phys. Chem., 80: S55-S62(2006); https://doi.org/10.1134/S0036024406130103
  32. M. Monajjemi, J. Molecular Model., 20: (2014); https://doi.org/10.1007/s00894-014-2507-y
  33. M. Monajjemi and J.E. Boggs, J. Phys. Chem. A, 117: 1670–1684 (2013); https://doi.org/10.1021/jp312073q
  34. M. Monajjemi, M. Heshmata, and H.H. Haeria, Biochem., 71: S113–S122 (2006); https://doi.org/10.1134/S0006297906130190
  35. M. Monajjemi, Chemical Phys., 425: 29–45 (2013); https://doi.org/10.1016/j.chemphys.2013.07.014
  36. M. Monajjemi, Biophys. Chem., 207: 114–127 (2015); https://doi.org/10.1016/j.bpc.2015.10.003
  37. F. Mollaamin, and M. Monajjemi, Phys. Chem. Liquids, 50: 596–604 (2012); https://doi.org/10.1080/00319104.2011.646444
  38. L. Mahdavian, M. Monajjemi, and N. Mangkorntong, Fullerenes Nanotubes and Carbon Nanostructures, 17: 484–495 (2009); https://doi.org/10.1080/15363830903130044
  39. M. Monajjemi, J. Molecular Liquids, 230: 461–472(2017); https://doi.org/10.1016/j.molliq.2017.01.044
  40. M. Monajjemi, L. Mahdavian, and F. Mollaamin, Bull. Chem. Soc. Ethiopia, 22: 277–286 (2008); https://doi.org/10.4314/bcse.v22i2.61299
  41. M. Monajjemi, W.J. Robert, and J.E. Boggs, Chemical Physics, 433: 1–11 (2014); https://doi.org/10.1016/j.chemphys.2014.01.017
  42. H. Jalilian and M. Monajjemi, Jap. J. Appl. Phys., 54: 085101 (2015); https://doi.org/10.7567/JJAP.54.085101
  43. M. Monajjemi, Theoretical Chemistry Accounts, 134: 1–22 (2015); https://doi.org/10.1007/s00214-015-1668-9
  44. M. Monajjemi, F. Naderi, F. Mollaamin, and M. Khaleghian, J. Mexican Chem. Soc., 56: 207–211 (2012); https://doi.org/10.29356/jmcs.v56i2.323
  45. M. Monajjemi, S. Bagheri, and M.S. Moosavi, Molecules, 20: 21636–21657 (2015); https://doi.org/10.3390/molecules201219769
  46. M. Monajjemi, L. Mahdavian, F. Mollaamin, and B. Honarparvar, Fullerenes Nanotubes and Carbon Nanostructures, 18: 45–55(2010); https://doi.org/0.1080/15363830903291564
  47. M. Monajjemi, S. Ketabi, Z.M. Hashemian, and A. Amiri, Biochem., 71: 1–8 (2006); https://doi.org/10.1134/s0006297906130013
  48. A.R. Ilkhani and M. Monajjemi, Comput. Theoret. Chem., 1074: 19–25 (2015); https://doi.org/10.1016%2Fj.comptc.2015.10.006
  49. F. Mollaamin, J. Najafpour, S. Ghadami, M.S. Akrami, and M. Monajjemi, J. Comp. Theoret. Nanosci., 11: 1290–1298 (2014).
  50. M. Monajjemi, V.S. Lee, M. Khaleghian, B. Honarparvar, and F. Mollaamin, J. Phys. Chem. C, 11: 15315–15330 (2010); https://doi.org/10.1021/jp104274z
  51. F. Mollaamin, and M. Monajjemi, J. Comp. Theoret. Nanosci., 9, No. 4: 597–601 (2012); https://doi.org/10.1166/jctn.2012.2067
  52. S. Shahriari, N.S. Soofi, F. Farzi, R. Esmkhani, and M. Monajjemi, J. Comp. Theoret. Nanosci., 13, No. 5: 3070–3082 (2016); https://doi.org/10.1166/JCTN.2016.4959
  53. W. Geffcken and E. Berger, Deutsches Reichs Patent, 736: 411 (1939) (assigned to Jenaer Glaswerk Schott & Gen).
  54. C.H. Shek and G.M. Lin, Nanostruct. Mater., 11, No. 7: 831–835 (1999).
  55. S. Bruni, F. Cariati, M. Casu, A. Lai, A. Musinu, G. Piccaluga, and S. Solinas, Nanostruct. Mater., 11, No. 5: 573(1999).
  56. G. Herzberg, Van Nostrand Company (New York: 1945).
  57. C.V. Ramana, A. Mauger, F. Gendron, C.M. Julien, and K. Zaghib, J. Power Sources, 187, No. 2: 555–564 (2009); https://doi.org/10.1016/j.jpowsour.2008.11.042
  58. W. Paraguassu, P.T.C. Freire, V. Lemos, S.M. Lala, L.A. Montoro, and J.M. Rosolen, J. Raman Spectrosc., 36: 213 (2005); https://doi.org/10.1002/jrs.1278
  59. L. Popović, B. Manoun, D. de Waal, M.K. Nieuwoudt, and J.D. Comins, J. Raman Spectrosc., 34: 77 (2003); https://doi.org/10.1002/jrs.954
  60. E. Smith and G. Dent, Modern Raman Spectroscopy — A Practical Approach (John Wiley & Sons: 2005).
  61. D.S. Artem, L. Kozlovskiy, and M. Zdorovets, Crystals, 11, No. 7: 753 (2021); https://doi.org/10.3390/cryst11070753
  62. T. Ohzuku, T. Yanagawa, and M. Kouguchi, J. Power Sources, 68: 131–134 (1997); https://doi.org/10.1016/S0378-7753(97)02516-0
  63. N. Yabuuchi, S. Kumar, H.H. Li, V. Kim, and Y. Shao-Horn, J. Electrochem. Soc., 154: A566 (2007); https://doi.org/10.1149/1.2724734
  64. T. Ohzuku, A. Ueda, M. Nagayama, Y. Iwakoshi, and H.Komori, Electrochim. Acta, 38: 1159–1167 (1993); https://doi.org/10.1016/0013-4686(93)80046-3
  65. K.M. Shaju, G.V. Subba Rao, and B.V.R. Chowdari, Electrochim. Acta, 48, No. 2: 145–151 (2002); https://doi.org/10.1016/S0013-4686(02)00593-5
  66. G.M. Ehrlich, D. Linden, Handbook of Lithium-Ion Batteries (New York: McGraw-Hill: 2002), p. 35.
  67. Z.-G. Yang, J.-L. Zhang, M.C.W. Kintner-Meyer, X.-C. Lu, D.-W. Choi, J.P. Lemmon, and J. Liu, Chem. Rev., 111, No. 5: 3577–3613 (2011); https://doi.org/10.1021/cr100290v
  68. L. Li, S. Guangyao, X. Qizhen, D. Yanhuai, W. Chengwei, and G. Deshu, Mater. Chem. Phys., 100, Nos. 2–3: 236–240 (2004); https://doi.org/10.1016/j.matchemphys.2005.12.035

Creative Commons License
This work is licensed under a Creative Commons Attribution-NoDerivatives 4.0 International License
© G. V. Kurdyumov Institute for Metal Physics of the N.A.S. of Ukraine,