Improving the electrochemical performance of lithium- and manganese-rich layered cathodes through low-level zinc doping

Kadhem, Rafed Jawad

doi:10.37652/juaps.2026.164769.1664

[1] Goodenough JB, Park KS. The Li-Ion Rechargeable Battery: A Perspective. Journal of the American Chemical Society. 2013;135(4):1167-76. 10.1021/ja3091438

[2] Tarascon JM, Armand M. Issues and Challenges Facing Rechargeable Lithium Batteries. Nature. 2001;414(6861):359-67.10.1038/35104644

[3] Zhao S, Yan K, Zhang J, Sun B, Wang G. Reaction Mechanisms of Layered Lithium-Rich Cathode Materials for High-Energy Lithium-Ion Batteries. Angewandte Chemie International Edition. 2021;60(5):2208-20.10.1002/anie.202000262

[4] Darjazi H, Rezvani SJ, Brutti S, Nobili F. Improvement of Structural and Electrochemical Properties of NMC Layered Cathode Material by Combined Doping and Coating. Electrochimica Acta. 2022;404:139577.10.1016/j.electacta.2021.139577

[5] Nitta N, Wu F, Lee JT, Yushin G. Li-Ion Battery Materials: Present and Future. Materials Today. 2015;18(5):252-64.10.1016/j.mattod.2014.10.040

[6] Yan J, Huang H, Tong J, Li W, Liu X, Zhang H, et al. Recent Progress on the Modification of High Nickel Content NCM: Coating, Doping, and Single Crystallization. Interdisciplinary Materials. 2022;1(3):330-53.10.1002/idm2.12043

[7] Çetin B, Camtakan Z, Yuca N.Synthesis and Characterization of Li-Rich Cathode Material for Lithium-Ion Batteries.Materials Letters. 2020;273:127927. 10.1016/j.matlet.2020.127927

[8] Zhang K, Sheng H, Wu X, Fu L, Liu Z, Zhou C, et al. Improving Electrochemical Properties by Sodium Doping for Lithium-Rich Layered Oxides. ACS Applied Energy Materials. 2020;3(9):8953-9. 10.1021/acsaem.0c01402

[9] Hendrickx M, Paulus A, Kirsanova MA, Van Bael MK, Abakumov AM, Hardy A, et al. The Influence of Synthesis Method on the Local Structure and Electrochemical Properties of Li-Rich/Mn-Rich NMC Cathode Materials for Li-Ion Batteries. Nanomaterials. 2022;12(13):2269. 10.3390/nano12132269

[10] Jeong S, Park S, Park J, Beak M, Lee J, Kwon EE, et al. The Enhancement of Cyclability of Ni-Rich LiNi0.9Co0.05−xMn0.05Znx Cathode Materials by the Substitution of Zn for Co. International Journal of Energy Research. 2022;46(13):19177-89. 10.1002/er.8178

[11] Shi Y, Kim K, Xing Y, Millonig A, Kim B, Wang L, et al.Facile and Scalable Dry Surface Doping Technique to Enhance the Electrochemical Performance of LiNi0.64Mn0.2Co0.16O2 Cathode Materials. Journal of Materials Chemistry A. 2020;8(38):19866-72. 10.1039/D0TA07779H

[12] Sanad MMS, Meselhy NK, El-Boraey HA, Toghan A. Controllable Engineering of New ZnAl2O4-Decorated LiNi0.8Mn0.1Co0.1O2 Cathode Materials for High-Performance Lithium-Ion Batteries. Journal of Materials Research and Technology. 2023;23:1528-42.10.1016/j.jmrt.2023.01.102

[13] Vanaphuti P, Chen J, Cao J, Bigham K, Chen B, Yang L, et al. Enhanced Electrochemical Performance of the Lithium-Manganese-Rich Cathode for Li-Ion Batteries with Na and F Codoping.ACS Applied Materials & Interfaces. 2019;11(41):37842-9.10.1021/acsami.9b13838

[14] Ahmed BR, Reyhani A, Khanlary MR, Mortazavi SZ. Investigation of the Synergetic Effects of GO and Zn on the Electrochemical Properties of Li[Li0.20Mn0.54Ni0.13Co0.13]O2 Cathode Material. Chemical Methodologies. 2025;9(9):737-50. 10.48309/chemm.2025.509286.1912

[15] Farshori NN, Al-Oqail MM, Al-Sheddi ES, Al-Massarani SM, Saquib Q, Siddiqui MA, et al. Green Synthesis of Silver Nanoparticles Using Phoenix dactylifera Seed Extract and Its Anticancer Effect Against Human Lung Adenocarcinoma Cells. Journal of Drug Delivery Science and Technology. 2022;70:103260.10.1016/j.jddst.2022.103260

[16] Echegaray-Ugarte TS, Cespedes-Loayza AL, Cruz-Loayza JL, Huayapa-Yucra LA, Cruz I, de Carvalho JC, et al. Green Synthesis of Silver Nanoparticles Mediated by Punica granatum Peel Waste: An Effective Additive for Natural Rubber Latex Nanofibers Enhancement. Polymers. 2024;16(11):1531.10.3390/polym16111531

[17] Ikemoto Y, Harada Y, Tanaka M, Nishimura Sn, Murakami D, Kurahashi N, et al. Infrared Spectra and Hydrogen-Bond Configurations of Water Molecules at the Interface of Water-Insoluble Polymers under Humidified Conditions. The Journal of Physical Chemistry B. 2022;126(22):4143-51. 10.1021/acs.jpcb.2c01702

[18] Dai F, Zhuang Q, Huang G, Deng H, Zhang X. Infrared Spectrum Characteristics and Quantification of OH Groups in Coal. ACS Omega. 2023;8(19):17064-76.10.1021/acsomega.3c01336

[19] Hashem AM, Abdel-Ghany AE, Scheuermann M, Indris S, Ehrenberg H, Mauger A, et al. Doped Nanoscale NMC333 as Cathode Materials for Li-Ion Batteries.Materials. 2019;12(18):2899. 10.3390/ma12182899

[20] Yavarinasab A, Abedini M, Tahmooressi H, Janfaza S, Tasnim N, Hoorfar M.Potentiodynamic Electrochemical Impedance Spectroscopy of Polyaniline-Modified Pencil Graphite Electrodes for Selective Detection of Biochemical Trace Elements.Polymers. 2022;14(1):31. 10.3390/polym14010031

[21] Kim C, Jang I. Application of Electrochemical Impedance Spectroscopy for Diagnostics in Fuel Cells, Electrolyzers, and Batteries.ChemElectroChem. 2025;12(11):e202500005. 10.1002/celc.202500005

[22] Kasper M, Moertelmaier M, Ragulskis M, Al-Zubaidi R-Smith N, Angerer J, Aufreiter M, et al.Calibrated Electrochemical Impedance Spectroscopy and Time-Domain Measurements of a 7 kWh Automotive Lithium-Ion Battery Module with 396 Cylindrical Cells.Batteries & Supercaps. 2023;6(2):e202200415. 10.1002/batt.202200415

[23] Celeste A, Brescia R, Gigli L, Plaisier JR, Pellegrini V, Silvestri L, et al.Unravelling Structural Changes of the Li1.2Mn0.54Ni0.13Co0.13O2 Lattice upon Cycling in Lithium Cell.Materials Today Sustainability. 2023;21:100277.10.1016/j.mtsust.2022.100277

[24] Xu Y, Cui Q. Nb-Doped Li1.20 [Mn0.54Ni0.13Co0.13]O2 Cathode Material with Enhanced Electrochemical Properties for Lithium-Ion Batteries. International Journal of Electrochemical Science. 2020;15(1):803-15. 10.20964/2020.01.47

[25] Lu Y, Shi S, Yang F, Zhang T, Niu H, Wang T. Mo-Doping for Improving the ZrF4-Coated Li[Li0.20Mn0.54Ni0.13Co0.13]O2 as High-Performance Cathode Materials in Lithium-Ion Batteries. Journal of Alloys and Compounds. 2018;767:23-33.10.1016/j.jallcom.2018.07.068

[26] Bai R, Zhao Y, Lu C, Meng Y, Gao W, Wang Y, et al.Sonochemical Synthesis and Electrochemical Performance of Reduced Graphene Oxide/Cerium Dioxide Nanocomposites. Journal of Chemical Research. 2023;47(2):17475198231158745. 10.1177/17475198231158745

	Improving the electrochemical performance of lithium- and manganese-rich layered cathodes through low-level zinc doping
Journal of University of Anbar for Pure Science
Volume 20, Issue 2, August 2026, Pages 232-242 PDF (1.67 M)
Document Type: Research Paper
DOI: 10.37652/juaps.2026.164769.1664
Author
Rafed Jawad Kadhem^*
University of Isfahan, Faculty of Physics, Department of Condensed Matter Physics, Iran
Abstract
In this study, Li [Li0.20Mn0.54Ni0.13Co0.13−xZnx] O2 samples with zinc doping levels of x = 0, 0.02, and 0.05 were synthesized using the sol-gel method. Structural characterization was performed using field-emission scanning electron microscopy (FESEM), Fourier-transform infrared spectroscopy (FTIR), Raman spectroscopy, and X-ray diffraction (XRD). The results showed that partial substitution with zinc increased the lattice parameters and reduced the crystallite size. Notably, the layered crystal structure remained unchanged, retaining the α NaFeO2 structure. These structural modifications improved lithium-ion transport without significantly altering the overall morphology. Electrochemical evaluation revealed that zinc doping improved charge-transfer kinetics and cycling stability. Cyclic voltammetry showed sharper and more intense redox peaks, indicating reduced polarization. Electrochemical impedance spectroscopy demonstrated a decrease in charge-transfer resistance from 317.4Ω for the undoped sample to 135Ω and 118Ω for the doped compositions. Galvanostatic charge-discharge tests showed that zinc doping increased the discharge capacity to 283.6 and 298.7 mAhg−1 compared with 249.8mAhg−1 for the undoped material, while also improving Coulombic efficiency. These findings confirm that minor zinc substitution can enhance structural stability and reduce interfacial resistance, suggesting a promising approach for improving the electrochemical performance, energy density, and cycling life of lithium-ion battery cathode materials.
Keywords
Electrochemical performance; Energy storage; Lithium-ion battery; Lithium and manganese-rich layered cathode; Zn doping

References
[1] Goodenough JB, Park KS. The Li-Ion Rechargeable Battery: A Perspective. Journal of the American Chemical Society. 2013;135(4):1167-76. 10.1021/ja3091438 [2] Tarascon JM, Armand M. Issues and Challenges Facing Rechargeable Lithium Batteries. Nature. 2001;414(6861):359-67.10.1038/35104644 [3] Zhao S, Yan K, Zhang J, Sun B, Wang G. Reaction Mechanisms of Layered Lithium-Rich Cathode Materials for High-Energy Lithium-Ion Batteries. Angewandte Chemie International Edition. 2021;60(5):2208-20.10.1002/anie.202000262 [4] Darjazi H, Rezvani SJ, Brutti S, Nobili F. Improvement of Structural and Electrochemical Properties of NMC Layered Cathode Material by Combined Doping and Coating. Electrochimica Acta. 2022;404:139577.10.1016/j.electacta.2021.139577 [5] Nitta N, Wu F, Lee JT, Yushin G. Li-Ion Battery Materials: Present and Future. Materials Today. 2015;18(5):252-64.10.1016/j.mattod.2014.10.040 [6] Yan J, Huang H, Tong J, Li W, Liu X, Zhang H, et al. Recent Progress on the Modification of High Nickel Content NCM: Coating, Doping, and Single Crystallization. Interdisciplinary Materials. 2022;1(3):330-53.10.1002/idm2.12043 [7] Çetin B, Camtakan Z, Yuca N.Synthesis and Characterization of Li-Rich Cathode Material for Lithium-Ion Batteries.Materials Letters. 2020;273:127927. 10.1016/j.matlet.2020.127927 [8] Zhang K, Sheng H, Wu X, Fu L, Liu Z, Zhou C, et al. Improving Electrochemical Properties by Sodium Doping for Lithium-Rich Layered Oxides. ACS Applied Energy Materials. 2020;3(9):8953-9. 10.1021/acsaem.0c01402 [9] Hendrickx M, Paulus A, Kirsanova MA, Van Bael MK, Abakumov AM, Hardy A, et al. The Influence of Synthesis Method on the Local Structure and Electrochemical Properties of Li-Rich/Mn-Rich NMC Cathode Materials for Li-Ion Batteries. Nanomaterials. 2022;12(13):2269. 10.3390/nano12132269 [10] Jeong S, Park S, Park J, Beak M, Lee J, Kwon EE, et al. The Enhancement of Cyclability of Ni-Rich LiNi0.9Co0.05−xMn0.05Znx Cathode Materials by the Substitution of Zn for Co. International Journal of Energy Research. 2022;46(13):19177-89. 10.1002/er.8178 [11] Shi Y, Kim K, Xing Y, Millonig A, Kim B, Wang L, et al.Facile and Scalable Dry Surface Doping Technique to Enhance the Electrochemical Performance of LiNi0.64Mn0.2Co0.16O2 Cathode Materials. Journal of Materials Chemistry A. 2020;8(38):19866-72. 10.1039/D0TA07779H [12] Sanad MMS, Meselhy NK, El-Boraey HA, Toghan A. Controllable Engineering of New ZnAl2O4-Decorated LiNi0.8Mn0.1Co0.1O2 Cathode Materials for High-Performance Lithium-Ion Batteries. Journal of Materials Research and Technology. 2023;23:1528-42.10.1016/j.jmrt.2023.01.102 [13] Vanaphuti P, Chen J, Cao J, Bigham K, Chen B, Yang L, et al. Enhanced Electrochemical Performance of the Lithium-Manganese-Rich Cathode for Li-Ion Batteries with Na and F Codoping.ACS Applied Materials & Interfaces. 2019;11(41):37842-9.10.1021/acsami.9b13838 [14] Ahmed BR, Reyhani A, Khanlary MR, Mortazavi SZ. Investigation of the Synergetic Effects of GO and Zn on the Electrochemical Properties of Li[Li0.20Mn0.54Ni0.13Co0.13]O2 Cathode Material. Chemical Methodologies. 2025;9(9):737-50. 10.48309/chemm.2025.509286.1912 [15] Farshori NN, Al-Oqail MM, Al-Sheddi ES, Al-Massarani SM, Saquib Q, Siddiqui MA, et al. Green Synthesis of Silver Nanoparticles Using Phoenix dactylifera Seed Extract and Its Anticancer Effect Against Human Lung Adenocarcinoma Cells. Journal of Drug Delivery Science and Technology. 2022;70:103260.10.1016/j.jddst.2022.103260 [16] Echegaray-Ugarte TS, Cespedes-Loayza AL, Cruz-Loayza JL, Huayapa-Yucra LA, Cruz I, de Carvalho JC, et al. Green Synthesis of Silver Nanoparticles Mediated by Punica granatum Peel Waste: An Effective Additive for Natural Rubber Latex Nanofibers Enhancement. Polymers. 2024;16(11):1531.10.3390/polym16111531 [17] Ikemoto Y, Harada Y, Tanaka M, Nishimura Sn, Murakami D, Kurahashi N, et al. Infrared Spectra and Hydrogen-Bond Configurations of Water Molecules at the Interface of Water-Insoluble Polymers under Humidified Conditions. The Journal of Physical Chemistry B. 2022;126(22):4143-51. 10.1021/acs.jpcb.2c01702 [18] Dai F, Zhuang Q, Huang G, Deng H, Zhang X. Infrared Spectrum Characteristics and Quantification of OH Groups in Coal. ACS Omega. 2023;8(19):17064-76.10.1021/acsomega.3c01336 [19] Hashem AM, Abdel-Ghany AE, Scheuermann M, Indris S, Ehrenberg H, Mauger A, et al. Doped Nanoscale NMC333 as Cathode Materials for Li-Ion Batteries.Materials. 2019;12(18):2899. 10.3390/ma12182899 [20] Yavarinasab A, Abedini M, Tahmooressi H, Janfaza S, Tasnim N, Hoorfar M.Potentiodynamic Electrochemical Impedance Spectroscopy of Polyaniline-Modified Pencil Graphite Electrodes for Selective Detection of Biochemical Trace Elements.Polymers. 2022;14(1):31. 10.3390/polym14010031 [21] Kim C, Jang I. Application of Electrochemical Impedance Spectroscopy for Diagnostics in Fuel Cells, Electrolyzers, and Batteries.ChemElectroChem. 2025;12(11):e202500005. 10.1002/celc.202500005 [22] Kasper M, Moertelmaier M, Ragulskis M, Al-Zubaidi R-Smith N, Angerer J, Aufreiter M, et al.Calibrated Electrochemical Impedance Spectroscopy and Time-Domain Measurements of a 7 kWh Automotive Lithium-Ion Battery Module with 396 Cylindrical Cells.Batteries & Supercaps. 2023;6(2):e202200415. 10.1002/batt.202200415 [23] Celeste A, Brescia R, Gigli L, Plaisier JR, Pellegrini V, Silvestri L, et al.Unravelling Structural Changes of the Li1.2Mn0.54Ni0.13Co0.13O2 Lattice upon Cycling in Lithium Cell.Materials Today Sustainability. 2023;21:100277.10.1016/j.mtsust.2022.100277 [24] Xu Y, Cui Q. Nb-Doped Li1.20 [Mn0.54Ni0.13Co0.13]O2 Cathode Material with Enhanced Electrochemical Properties for Lithium-Ion Batteries. International Journal of Electrochemical Science. 2020;15(1):803-15. 10.20964/2020.01.47 [25] Lu Y, Shi S, Yang F, Zhang T, Niu H, Wang T. Mo-Doping for Improving the ZrF4-Coated Li[Li0.20Mn0.54Ni0.13Co0.13]O2 as High-Performance Cathode Materials in Lithium-Ion Batteries. Journal of Alloys and Compounds. 2018;767:23-33.10.1016/j.jallcom.2018.07.068 [26] Bai R, Zhao Y, Lu C, Meng Y, Gao W, Wang Y, et al.Sonochemical Synthesis and Electrochemical Performance of Reduced Graphene Oxide/Cerium Dioxide Nanocomposites. Journal of Chemical Research. 2023;47(2):17475198231158745. 10.1177/17475198231158745
Statistics Article View: 127 PDF Download: 344