Enhancing Lithium-Ion Battery Performance With Ultra-Thin LiF Coating: A Study on Surface Vapor Deposition for LiNi_0.9Co_0.05Mn_0.05O₂ Cathode Material Stabilization

Abstract

High-nickel ternary cathode (HNCM) materials are regarded as the primary choice for lithium-ion batteries (LIBs) due to their high energy density. However, their development is limited by lithium-nickel mixing, microcrack generation, and surface side reactions. Herein, a combined roll-to-roll and vacuum vapor deposition process is used to prepare LiNi_0.9Co_0.05Mn_0.05O₂ (NCM9055) cathode material with a dense, ultrathin, and robust lithium fluoride (LiF) protective layer. Compared with traditional methods, this approach allows precise control over the thickness and rate of the deposited LiF layer, producing a uniform and robust protective layer that enhances surface stability. This approach not only effectively reduces direct contact between the electrolyte and the electrode surface, mitigating corrosion and side reactions, but also strengthens the structural integrity of the cathode, thereby significantly improving cycling stability. The NCM9055 with a 10 nm LiF layer exhibits enhanced electrochemical performance, especially at cut-off voltages of 4.3 and 4.5 V, and also excellent cycling performance at 1 C. Additionally, the introduction of the LiF layer improves the thermal stability of NCM9055, further enhancing the safety of high-nickel batteries. This study not only demonstrates the combination of roll-to-roll processing and vacuum vapor deposition as a fast and effective modification technique but also highlights the advantages of vacuum vapor deposition in forming a homogeneous and robust LiF layer, which is essential for rapid production and for improving the safety and energy density of HNCM materials in advanced LIBs.

Keywords

high-nickel ternary cathode material / LiF coating / lithium-ion batteries / vacuum vapor deposition

References

[1] M. A. Rendón, C. D. Sánchez R., J. Gallo M., and A. H. Anzai, “Aircraft Hybrid-Electric Propulsion: Development Trends, Challenges and Opportunities,” Journal of Control, Automation and Electrical Systems 32 (2021): 1244-1268, https://doi.org/10.1007/s40313-021-00740-x.

[2] C. P. Grey and D. S. Hall, “Prospects for Lithium-Ion Batteries and Beyond—A 2030 Vision,” Nature Communications 11 (2020): 6279, https://doi.org/10.1038/s41467-020-19991-4.

[3] F. M. N. U. Khan, M. G. Rasul, A. S. M. Sayem, and N. Mandal, “Maximizing Energy Density of Lithium-Ion Batteries for Electric Vehicles: A Critical Review,” Energy Reports 9 (2023): 11-21, https://doi.org/10.1016/j.egyr.2023.08.069.

[4] M. Armand, P. Axmann, D. Bresser, et al., “Lithium-Ion Batteries—Current State of the Art and Anticipated Developments,” Journal of Power Sources 479 (2020): 228708, https://doi.org/10.1016/j.jpowsour.2020.228708.

[5] P. Yan, J. Zheng, M. Gu, J. Xiao, J.-G. Zhang, and C.-M. Wang, “Intragranular Cracking as a Critical Barrier for High-Voltage Usage of Layer-Structured Cathode for Lithium-Ion Batteries,” Nature Communications 8 (2017): 14101, https://doi.org/10.1038/ncomms14101.

[6] D. Hu, Y. Su, L. Chen, et al., “The Mechanism of Side Reaction Induced Capacity Fading of Ni-Rich Cathode Materials for Lithium Ion Batteries,” Journal of Energy Chemistry 58 (2021): 1-8, https://doi.org/10.1016/j.jechem.2020.09.031.

[7] S. J. Shi, J. P. Tu, Y. Y. Tang, et al., “Enhanced Electrochemical Performance of LiF-Modified LiNi_1/3Co_1/3Mn_1/3O₂ Cathode Materials for Li-ion Batteries,” Journal of Power Sources 225 (2013): 338-346, https://doi.org/10.1016/j.jpowsour.2012.10.065.

[8] X. Xiong, Z. Wang, X. Yin, H. Guo, and X. Li, “A Modified LiF Coating Process to Enhance the Electrochemical Performance Characteristics of LiNi_0.8Co_0.1Mn_0.1O₂ Cathode Materials,” Materials Letters 110 (2013): 4-9, https://doi.org/10.1016/j.matlet.2013.07.098.

[9] K. Meng, Z. Wang, H. Guo, X. Li, and D. Wang, “Improving the Cycling Performance of LiNi_0.8Co_0.1Mn_0.1O₂ by Surface Coating With Li₂TiO₃,” Electrochimica Acta 211 (2016): 822-831, https://doi.org/10.1016/j.electacta.2016.06.110.

[10] X. Zhang, F. Ma, G. Wei, Z. Lei, and J. Qu, “Improvement of Electrochemical Performance of LiNi_0.8Co_0.1Mn_0.1O₂ Cathode Material via Li_2.09W_0.9Nb_0.1O₄ Li-Ion Conductive Coating Layer,” Journal of Solid State Electrochemistry 24 (2020): 2301-2313, https://doi.org/10.1007/s10008-020-04742-8.

[11] J. Li, J. Wang, X. Lu, et al., “Enhancing High-Potential Stability of Ni-Rich LiNi_0.8Co_0.1Mn_0.1O₂ Cathode With PrF₃ Coating,” Ceramics International 47 (2021): 6341-6351, https://doi.org/10.1016/j.ceramint.2020.10.213.

[12] T. He, L. Chen, Y. Su, et al., “The Effects of Alkali Metal Ions With Different Ionic Radii Substituting in Li Sites on the Electrochemical Properties of Ni-Rich Cathode Materials,” Journal of Power Sources 441 (2019): 227195, https://doi.org/10.1016/j.jpowsour.2019.227195.

[13] A. Saha, O. Shalev, S. Maiti, et al., “Evolution of Ternary Li_xSn_yO_z Artificial Cathode-Electrolyte Interphase (ACEI) Through ALD: A Surface Strengthened NCM811 With Enhanced Electrochemical Performances for Li-Ion Batteries,” Materials Today Energy 31 (2023): 101207, https://doi.org/10.1016/j.mtener.2022.101207.

[14] A. Yano, M. Shikano, A. Ueda, H. Sakaebe, and Z. Ogumi, “LiCoO₂ Degradation Behavior in the High-Voltage Phase Transition Region and Improved Reversibility With Surface Coating,” Journal of the Electrochemical Society 164 (2017): A6116-A6122, https://doi.org/10.1149/2.0181701jes.

[15] L. A. Riley, S. Van Atta, A. S. Cavanagh, et al., “Electrochemical Effects of ALD Surface Modification on Combustion Synthesized LiNi_1/3Mn_1/3Co_1/3O₂ as a Layered-Cathode Material,” Journal of Power Sources 196 (2011): 3317-3324, https://doi.org/10.1016/j.jpowsour.2010.11.124.

[16] Y. Xu, L. Yao, H. Yuan, et al., “Surface Fluorination of Nickel Nanowires Enabling LiF-Rich Nanoscale Solid Electrolyte Interface for Stable Lithium Anodes,” Chemical Engineering Journal 496 (2024): 153873, https://doi.org/10.1016/j.cej.2024.153873.

[17] S. Ma, X. Zhang, S. Li, et al., “In Situ Formed LiNi_0.8Co_0.1Mn_0.1O₂@LiF Composite Cathode Material With High Rate Capability and Long Cycling Stability for Lithium-Ion Batteries,” Ionics 26 (2020): 2165-2176, https://doi.org/10.1007/s11581-019-03353-2.

[18] U.-H. Kim, G. T. Park, B. K. Son, et al., “Heuristic Solution for Achieving Long-Term Cycle Stability for Ni-Rich Layered Cathodes at Full Depth of Discharge,” Nature Energy 5 (2020): 860-869, https://doi.org/10.1038/s41560-020-00693-6.

[19] T. Ohzuku, A. Ueda, and M. Nagayama, “Electrochemistry and Structural Chemistry of LiNiO₂ (R3m) for 4 Volt Secondary Lithium Cells,” Journal of the Electrochemical Society 140 (1993): 1862, https://doi.org/10.1149/1.2220730.

[20] J. Gao, Y. Zou, J. Han, et al., “Regulating the Electrode-Electrolyte Interfaces of Lithium-High Nickel Batteries via a Multifunctional Additive,” ACS Applied Materials & Interfaces 16 (2024): 11506-11515, https://doi.org/10.1021/acsami.3c17736.

[21] P. Kaspar, D. Sobola, K. Částková, et al., “Case Study of Polyvinylidene Fluoride Doping by Carbon Nanotubes,” Materials 14 (2021): 1428, https://doi.org/10.3390/ma14061428.

[22] B. Chu, R. Xu, G. Li, et al., “Simultaneous B/W Dual Coating on Ultra-High Nickel Single Crystal Cathode Material for Lithium-Ion Batteries,” Journal of Power Sources 577 (2023): 233260, https://doi.org/10.1016/j.jpowsour.2023.233260.

[23] L. Wang, G. Liu, R. Xu, et al., “Enabling an Intrinsically Safe and High-Energy-Density 4.5 V-Class Lithium-Ion Battery With Synergistically Incorporated Fast Ion Conductors,” Advanced Energy Materials 13 (2023): 2203999, https://doi.org/10.1002/aenm.202203999.

[24] T. Ohzuku, A. Ueda, and M. Nagayama, “Electrochemistry and Structural Chemistry of LiNiO₂ (R3m) for 4 Volt Secondary Lithium Cells,” Journal of the Electrochemical Society 140 (1993): 1862-1870, https://doi.org/10.1149/1.2220730.

[25] S. Li, Z. Huang, F. Liu, et al., “Unveiling the Role of Fluorinated Interface on Anionic Redox Chemistry in Li-Rich Layered Oxide Cathode Materials Towards High-Energy Li Metal Batteries,” Energy Storage Materials 71 (2024): 103671, https://doi.org/10.1016/j.ensm.2024.103671.

[26] K. Fang, Q. Xie, C. Wang, et al., “Understanding the Feasibility of Manganese Substitution for Cobalt in the Synthesis of Nickel-Rich and Cobalt-Free Cathode Materials,” ACS Applied Energy Materials 4 (2021): 7190-7200, https://doi.org/10.1021/acsaem.1c01292.

[27] S. Liu, H. Yue, Y. Mo, et al., “Retarding the Capacity Fading and Voltage Decay of Li-Rich Mn-Based Cathode Materials via a Compatible Layer Coating for High-Performance Lithium-Ion Batteries,” RSC Advances 14 (2024): 26142-26151, https://doi.org/10.1039/D4RA03660C.

[28] K. C. Mahesh, H. Manjunatha, T. V. Venkatesha, and G. S. Suresh, “Study of Lithium Ion Intercalation/De-Intercalation Into LiNi_1/3Mn_1/3Co_1/3O₂ in Aqueous Solution Using Electrochemical Impedance Spectroscopy,” Journal of Solid State Electrochemistry 16 (2012): 3011-3025, https://doi.org/10.1007/s10008-012-1739-y.

[29] R.-Q. Su, J.-J. Zhu, Q.-R. Kong, and X. Yao, “High-Performance 0.75Li₃V₂(PO₄)₃·0.25Li₃PO₄/C Composite Cathode for Lithium-Ion Batteries,” Rare Metals 43 (2024): 6081-6087, https://doi.org/10.1007/s12598-024-02896-2.

[30] Y.-S. Zhao, F.-F. Wang, J.-C. Wang, P.-F. Wang, T.-F. Yi, and J.-H. Zhang, “Rapid Lithium-Ion Insertion/Extraction and Migration Behavior of Na₂WO₄-Encapsulated Lithium-Rich Layered Oxide Cathode,” Rare Metals 43 (2024): 3647-3660, https://doi.org/10.1007/s12598-024-02633-9.

[31] H.-H. Ryu, K.-J. Park, C. S. Yoon, and Y.-K. Sun, “Capacity Fading of Ni-Rich Li[Ni_xCo_yMn_1-x-y]O₂ (0.6 ≤ x ≤ 0.95) Cathodes for High-Energy-Density Lithium-Ion Batteries: Bulk or Surface Degradation?,” Chemistry of Materials 30 (2018): 1155-1163, https://doi.org/10.1021/acs.chemmater.7b05269.

[32] Q.-T. Liao, S.-J. Guo, M.-Y. Qi, et al., “The Genesis and Control of Microcracks in Nickel-Rich Cathode Materials for Lithium-Ion Batteries,” Sustainable Energy & Fuels 7 (2023): 4805-4824, https://doi.org/10.1039/D3SE00844D.

[33] Z. Qiu, Y. Zhang, P. Dong, S. Xia, and Y. Yao, “A Facile Method for Synthesis of LiNi_0.8Co_0.15Al_0.05O₂ Cathode Material,” Solid State Ionics 307 (2017): 73-78, https://doi.org/10.1016/j.ssi.2017.04.011.

[34] H. Zhao, Y. Bai, H. Jin, J. Zhou, X. Wang, and C. Wu, “Unveiling Thermal Decomposition Kinetics of Single-Crystalline Ni-Rich LiNi_0.88Co_0.07Mn_0.05O₂ Cathode for Safe Lithium-Ion Batteries,” Chemical Engineering Journal 435 (2022): 134927, https://doi.org/10.1016/j.cej.2022.134927.

[35] Y.-S. Duh, C.-Y. Lee, Y.-L. Chen, and C.-S. Kao, “Characterization on the Exothermic Behaviors of Cathode Materials Reacted With Ethylene Carbonate in Lithium-Ion Battery Studied by Differential Scanning Calorimeter (DSC),” Thermochimica Acta 642 (2016): 88-94, https://doi.org/10.1016/j.tca.2016.09.007.

RIGHTS & PERMISSIONS

2025 The Author(s). Battery Energy published by Xijing University and John Wiley & Sons Australia, Ltd.