Boosting the electrochemical performance of spinel LiMn2O4 cathode material via copper surface decoration
Original scientific paper
DOI:
https://doi.org/10.5599/jese.3388Keywords:
Lithium-ion batteries, lithium manganese oxide, surface metal modifier, capacity fading, charge-dischargeAbstract
The spinel LiMn₂O₄ (LMO) is a promising cathode material for lithium-ion batteries due to its low cost, abundance, relatively low toxicity, and straightforward processing. Despite these advantages, its practical application is hindered by capacity fading resulting from Jahn-Teller distortion and manganese dissolution. In this study, LMO was synthesized using the glycine-nitrate combustion method and subsequently surface-modified with metallic copper through electroless deposition. Characterization of the Cu-decorated LMO was conducted using X-ray diffraction, elemental analysis, scanning electron microscopy and X-ray photoelectron spectroscopy. Cyclic voltammetry indicated increased redox peak intensities and enhanced electrochemical reversibility, as evidenced by reduced peak-to-peak potential differences for LMO@Cu. At 0.1C, LMO@Cu achieved an initial discharge capacity of 114.3 mAh g⁻¹, surpassing the 103.8 mAh g⁻¹ observed for pristine LMO. Rate-capability assessments from 0.1C to 10C showed consistently higher discharge capacities for LMO@Cu, with the most significant improvement at 10C, where LMO@Cu and LMO delivered approximately 45 and 8 mAh g⁻¹, respectively. At 55 °C, LMO@Cu maintained 90.44 % capacity retention after 50 cycles, compared to 85.01 % for LMO. The improved performance is attributed to enhanced electronic transport and electrochemical kinetics facilitated by the dispersed copper phase.
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References
[1] D. Linden, T. B. Reddy, Handbook of Batteries, 3rd Ed., McGraw-Hill, New York, USA, 2001. ISBN: 978-0071359788
[2] R. M. Dell, D. A. J. Rand, Understanding Batteries, Royal Society of Chemistry, Cambridge, UK, 2001. ISBN: 978-0854046058
[3] G. Pistoia, D. Zane, Y. Zhang. Some Aspects of Electrochemistry in the 4 Volt Range, Journal of The Electrochemical Society 142 (1995) 2551-2557. http://dx.doi.org/10.1149/1.2050052
[4] T. Aoshima, K. Okahara, C. Kiyohara, K. Shizuka, Mechanisms of Manganese Spinels Dissolution and Capacity Fade at High Temperature, Journal of Power Sources 97-98 (2001) 377-380. http://dx.doi.org/10.1016/S0378-7753(01)00551-1
[5] H. Yang, L. Yan, J. Qin, Y. Wang, N. Hu, T. Zhou. Thermal Stress Synergizes Oxygen Vacancies Alleviate Jahn-Teller Distortion in Lithium Manganate Cathode, Advanced Functional Materials 36(8) (2026) e15317. https://doi.org/10.1002/adfm.202515317
[6] Y. Yu, Y. Duan, Y. Guo, R. Liu, Enhanced high-rate performance of LiMn2O4 cathode via earth-abundant element-doping for lithium-ion batteries, Electrochimica Acta 544 (2025) 147673. https://doi.org/10.1016/j.electacta.2025.147673
[7] F. Paparoni, E. Mijit, H. Darjazi, F. Nobili, A. Zitolo, A. Di Cicco, R. Parmar, R. Gunnella, S. J. Rezvani, Oxide Coating Role on the Bulk Structural Stability of Active LiMn2O4 Cathodes, Journal of Physical Chemistry C 127 (2023) 8649-8656. https://doi.org/10.1021/acs.jpcc.3c00342
[8] Y. Tesfamhret, H. Liu, Z. Chai, E. Berg, R. Younesi, On the Manganese Dissolution Process from LiMn2O4 Cathode Materials, ChemElectroChem 8 (2021) 1516-1523. https://doi.org/10.1002/celc.202001496
[9] Q. Ren, Y. Yuan, S. Wang. Interfacial Strategies for Suppression of Mn Dissolution in Rechargeable Battery Cathode Materials. ACS Applied Materials & Interfaces 14(20) (2022) 23022-23032. https://doi.org/10.1021/acsami.1c20406
[10] J. C. Hestenes, J. T. Sadowski, R. May, L. E. Marbella, Transition Metal Dissolution Mechanisms and Impacts on Electronic Conductivity in Composite LiNi0.5Mn1.5O4 Cathode Films, ACS Materials Au 3(2) (2023) 88-101. https://doi.org/10.1021/acsmaterialsau.2c00060
[11] Y. Xia, Y. Zhou, M. Yoshio, Capacity Fading on Cycling of 4 V Li /LiMn2O 4 Cells, Journal of The Electrochemical Society 144 (1997) 2593-2600. https://doi.org/10.1149/1.1837870
[12] D. Pasquier, A. Blyr, P. Courjal, D. Larcher, G. Amatucci, B. Gérand and J‐M. Tarascon, Mechanism for Limited 55°C Storage Performance of Li1.05Mn1.95O 4 Electrodes, Journal of The Electrochemical Society 146(2) (1999) 428-436. https://doi.org/10.1149/1.1391625
[13] G. Liu, S. Dai, H. Han, K. Liu, Enhanced Electrochemical Properties of LiMn2O4 Cathode Materials by Coating with ZnO, International Journal of Electrochemical Science 17 (2022) 220657. https://doi.org/10.20964/2022.06.60
[14] H. Liu, F. Yang, J. Guo, M. Xiang, H.Bai, R. Wang, C. Su, Facile combustion synthesis of amorphous Al2O3-coated LiMn2O4 cathode materials for high-performance Li-ion batteries, New Journal of Chemistry 45 (2021) 10534-10540. https://doi.org/10.1039/D1NJ01052B
[15] M. E. Çetintaşoğlu, O. Keleş, Effects of sonication power on electrochemical performance of ZrO2-decorated LiMn2O4 cathode material for LIBs, Bulletin of Materials Science 44 (2021) 109-115. https://doi.org/10.1007/s12034-021-02368-8
[16] T. Verhelle, A. Dhara, L. Henderick, M. Minjauw, L. De Taeye, J. Meersschaut, J. Dendooven, C. Detavernier, Atomic Layer Deposition of Lithium Borate and Lithium Borophosphate for Lithium-Ion Batteries, Chemistry of Materials 37 (2025) 687-696. https://doi.org/10.1021/acs.chemmater.4c02747
[17] H. Li, J. Pan, Y. Ping, J. Su, M. Fang, T. Chen, B. Pan, Z. Lu, Annealed SiO2 Protective Layer on LiMn2O4 for Enhanced Li-Ion Extraction from Brine, Nano Letters 23(22) (2023) 10458-10465. https://doi.org/10.1021/acs.nanolett.3c03136
[18] H. Şahan, H. Göktepe, Ş. Patat, A Novel Method to Improve the Electrochemical Performance of LiMn2O4 Cathode Active Material by CaCO3 Surface Coating, Journal of Materials Science & Technology 27 (2011) 415-420. https://doi.org/10.1016/S1005-0302(11)60084-4
[19] H. Şahan, H. Göktepe, Ş. Patat, A. Ülgen, Effect of the Cr2O3 coating on electrochemical properties of spinel LiMn2O4 as a cathode material for lithium battery applications, Solid State Ionics 181 (2010) 1437-1443. https://doi.org/10.1016/j.ssi.2010.08.008
[20] H. Şahan, F. Kılıç Dokan, A. Ülgen, Ş. Patat, Improvement of cycling stability of LiMn2O4 cathode by Fe2O3 surface modification for Li-ion battery, Ionics 20 (2014) 323-330. https://doi.org/10.1007/s11581-013-0987-x
[21] Y. Shang, X. Lin, X. Lu, T. Huang, A. Yu, Nano-TiO2(B) coated LiMn2O4 as cathode materials for lithium-ion batteries at elevated temperatures, Electrochimica Acta 156 (2015) 121-126. https://doi.org/10.1016/j.electacta.2015.01.024
[22] H. Şahan, H. Göktepe, Ş. Patat, A. Ülgen, Improvement of the electrochemical performance of LiMn2O4 cathode active material by lithium borosilicate (LBS) surface coating for lithium ion batteries, Journal of Alloys and Compounds 509 (2011) 4235-4241. https://doi.org/10.1016/j.jallcom.2011.01.054
[23] H. Göktepe, H. Şahan, Ş. Patat, Effect of silver and carbon double coating on the electrochemical performance of LiFePO4 cathode material for lithium ion batteries, International Journal of Hydrogen Energy 41 (2016) 9774-9779. https://doi.org/10.1016/j.ijhydene.2016.03.074
[24] S. M. Abbas, A. M. Hashem, A. E. Abdel-Ghany, E.H. Ismail, M. Kotlár, M. Winter, J. Li, C.M. Julien, Ag-Modified LiMn2O4 Cathode for Lithium-Ion Batteries: Coating Functionalization, Energies 13 (2020) 5194. https://doi.org/10.3390/en13195194
[25] R. Jiang, C. Cui, H. Ma, H. Ma, T. Chen, Study on the enhanced electrochemical performance of LiMn2O4 cathode material at 55 °C by the nano Ag-coating, Journal of Electroanalytical Chemistry 744 (2015) 69-76. https://doi.org/10.1016/j.jelechem.2015.02.016
[26] H. Sun, Y. Zhang, W. Li, B. Wang, Effects of Ag coating on the structural and electrochemical properties of LiNi0.8Co0.1Mn0.1O2 as cathode material for lithium ion batteries, Electrochimica Acta 327 (2019) 135054. https://doi.org/10.1016/j.electacta.2019.135054
[27] X. Li, K. Chang, S. M. Abbas, R. S. El-Tawil, A. E. Abdel-Ghany, A. M. Hashem, H. Wang, A. L. Coughlin, S. Zhang, A. Mauger, L. Zhu, C. M. Julien, Silver Nanocoating of LiNi0.8Co0.1Mn0.1O2 Cathode Material for Lithium-Ion Batteries, Micromachines 14(5) (2023) 907. https://doi.org/10.3390/mi14050907
[28] H. Chen, Y. Xiao, L. Wang, Y. Yang, Silicon nanowires coated with copper layer as anode materials for lithium-ion batteries, Journal of Power Sources 196 (2011) 6657-6662. https://doi.org/10.1016/j.jpowsour.2010.12.075
[29] S. Murugesan, J. T. Harris, B. A. Korgel, K. J. Stevenson, Copper-Coated Amorphous Silicon Particles as an Anode Material for Lithium-Ion Batteries, Chemistry of Materials 24 (2012) 1306-1315. https://doi.org/10.1021/cm2037475
[30] X. Wang, D. Liu, Q. Weng, J. Liu, Q. Liang, C. Zhang, Cu/Li4Ti5O12 scaffolds as superior anodes for lithium-ion batteries, NPG Asia Materials 7 (2015) e171. https://doi.org/10.1038/am.2015.23
[31] M. O. Güler, A. Erdas, D. Nalcı, H. Akbulut, Binary Cu/LiCr2/3V1/6Mn1/6O2 p-type semiconductor nanocomposite structures as cathode electrodes for Li-ion batteries, Materials Science in Semiconductor Processing 38 (2015) 392-396. https://doi.org/10.1016/j.mssp.2015.02.068
[32] Malvern Panalytical, HighScore. https://www.malvernpanalytical.com/en/products/category/software/x-ray-diffraction-software/highscore (Accessed 6.10.2026)
[33] Y. Zhang, H. Shin, J. Dong, M. Liu, Nanostructured LiMn2O4 prepared by a glycine-nitrate process for lithium-ion batteries, Solid State Ionics 171 (2004) 25-31. https://doi.org/10.1016/j.ssi.2004.04.008
[34] Y. L. Ding, J. Xie, G. S. Cao, T. J. Zhu, H.-M. Yu, X.-B. Zhao, Single-Crystalline LiMn2O4 Nanotubes Synthesized Via Template-Engaged Reaction as Cathodes for High-Power Lithium Ion Batteries, Advanced Functional Materials 21 (2011) 348-355. https://doi.org/10.1002/adfm.201001448
[35] K. Dokko, S. Horikoshi, T. Itoh, M. Nishizawa, M. Mohamedi, I.Uchida, Microvoltammetry for cathode materials at elevated temperatures: electrochemical stability of single particles, Journal of Power Sources 90 (2000) 109-115. https://doi.org/10.1016/S0378-7753(00)00456-0
[36] C. Tomon, S. Sarawutanukul, N. Phattharasupakun, S. Duangdangchote, P. Chomkhuntod, N. Joraleechanchai, M. Sawangphruk. Core-shell structure of LiMn2O4 cathode material reduces phase transition and Mn dissolution in Li-ion batteries. Communications Chemistry 5(1) (2022) 54. https://doi.org/10.1038/s42004-022-00670-y
[37] P. Ilango, K. Prasanna, S. Do, Y. N. Jo, C. W. Lee, Eco-friendly nitrogen-containing carbon encapsulated LiMn2O4 cathodes to enhance the electrochemical properties in rechargeable Li-ion batteries, Scientific Reports 6 (2016) 29826. https://doi.org/10.1038/srep29826
[38] A. J. Bard, L. R. Faulkner, Electrochemical Methods: Fundamentals and Applications, John Wiley & Sons, New York, USA, 2001, 385-400. ISBN: 978-0471043720
[39] L. L. Zhang, S. Duan, X. L. Yang, G. Peng, G. Liang, Y.-H. Huang, Y. Jiang, S.-B. Ni, M. Li, Reduced Graphene Oxide Modified Li2FeSiO4/C Composite with Enhanced Electrochemical Performance as Cathode Material for Lithium Ion Batteries, ACS Applied Materials & Interfaces 5 (2013) 12304-12309. https://doi.org/10.1021/am402434n
[40] X. Wang, H. Hao, J. Liu, T. Huang, A. Yu, A novel method for preparation of macroposous lithium nickel manganese oxygen as cathode material for lithium ion batteries, Electrochimica Acta 56 (2011) 4065-4069. https://doi.org/10.1016/j.electacta.2010.12.108
[41] M. Ma, A. N. Mansour, J. K. Ko, G. H. Waller, C. E. Hendricks, Characterization of Li Diffusion and Solid Electrolyte Interface for Li4Ti5O12 Electrode Cycled with an Organosilicon Additive Electrolyte, Journal of The Electrochemical Society 167 (2020) 110549. https://doi.org/10.1149/1945-7111/aba5d3
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Copyright (c) 2026 Halil Şahan, Ferhat Şanlı , Yusuf Taş , Yakup Yılmaz , Şaban Patat
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Erciyes Üniversitesi
Grant numbers FBG-2025-14576;FDK-2020-10421
