Achievement of Superhigh Discharge Capacity in Lithium Rich Oxide Cathode Materials via Modification of Localized Structure

Abstract

Owing to anionic redox, cathode materials containing layered Li-rich Mn-based oxides (LLOs) are promising for the development of next-generation lithium-ion batteries (LIBs) with a large energy density (~500–600 Wh·kg⁻¹). However, these LLOs are easily degraded during cycling, which limits their lifespan. So far, the degradation mechanism is still under debate. Herein, LLOs are post-treated through implantation with energetic Ti ion flux (Ti-LLO), which modifies the structure of LLOs both at the surface and within the bulk. Unlike the dominant R\bar{3}m phase (73.24%) observed in LLOs, the phase structure of Ti-LLO is altered, with Li-rich C2/m accounting for 67.72% in the bulk, alongside the formation of a thin (approximately 2 nm), uniform, and continuous Li-Ti-O spinel layer at the surface. Apart from phase structure changes, chemical valence states of transition metals and O, as well as their evolution, are analyzed and compared to charge transport kinetics to elucidate their contributions to the enhanced discharge capacity in Ti-LLOs. Besides, the role of the Li-Ti-O spinel layer at the surface in providing anticorrosion protection at the interface of LLOs/electrolyte during cycling is evaluated. As a result, we demonstrate that a superhigh discharge capacity (335.3 mAh·g⁻¹) at 0.1 C can be achieved, along with prolonged cycling stability (showing capacity retention of approximately 80% after 500 cycles at 1 C) through these modifications. Moreover, we confirmed the universality of the strategy by implanting other ions, which offers practical strategies for achieving high performance in LLO cathode materials through thermodynamics and kinetics pathways.

Keywords

ion implantation / lithium-ion batteries / lithium-rich Mn-based oxides / localized structure / superhigh discharge capacity

References

[1] T. Liu, T. Dong, M. Wang, et al., “Recycled Micro-Sized Silicon Anode for High-Voltage Lithium-Ion Batteries,” Nature Sustainability 7, no. 8 (2024): 1057–1066.

[2] L. Ma, N. Li, S. Zhou, X. Zhang, and K. Xie, “Lithium Battery-Powered Extreme Environments Exploring: Principle, Progress, and Perspective,” Advanced Energy Materials 14, no. 32 (2024): 2401157.

[3] X. Kong, R. Gu, Z. Jin, et al., “Maximizing Interface Stability in All-Solid-State Lithium Batteries Through Entropy Stabilization and Fast Kinetics,” Nature Communications 15, no. 1 (2024): 7247.

[4] S. Jin, X. Gao, S. Hong, et al., “Fast-Charge, Long-Duration Storage in Lithium Batteries,” Joule 8, no. 3 (2024): 746–763.

[5] Z. Wu, S. He, C. Zheng, et al., “Fabrication Pressures and Stack Pressures in Solid-State Battery,” eScience 4 (2024): 100247.

[6] S. Jiao, J. Wang, Y.-S. Hu, X. Yu, and H. Li, “High-Capacity Oxide Cathode Beyond 300 mAh/g,” ACS Energy Letters 8, no. 7 (2023): 3025–3037.

[7] X. Zhou, F. Hong, S. Wang, et al., “Precision Engineering of High-Performance Ni-Rich Layered Cathodes With Radially Aligned Microstructure Through Architectural Regulation of Precursors,” eScience 4 (2024): 100276.

[8] Y. Gao, S. Zhang, F. Zhao, et al., “Fluorinated Superionic Oxychloride Solid Electrolytes for High-Voltage All-Solid-State Lithium Batteries,” ACS Energy Letters 9, no. 4 (2024): 1735–1742.

[9] S. N. Lauro, J. N. Burrow, and C. B. Mullins, “Restructuring the Lithium-Ion Battery: A Perspective on Electrode Architectures,” eScience 3, no. 4 (2023): 100152.

[10] L. Wang, A. Mukherjee, C.-Y. Kuo, et al., “High-Energy All-Solid-State Lithium Batteries Enabled by Co-Free LiNiO₂ Cathodes With Robust Outside-In Structures,” Nature Nanotechnology 19, no. 2 (2024): 208–218.

[11] J. Chen, Y. Zhang, H. Lu, et al., “Electrolyte Solvation Chemistry to Construct an Anion-Tuned Interphase for Stable High-Temperature Lithium Metal Batteries,” eScience 3, no. 4 (2023): 100135.

[12] S. Wang, L. Zhang, Q. Zeng, et al., “Designing Polymer Electrolytes via Ring-Opening Polymerization for Advanced Lithium Batteries,” Advanced Energy Materials 14, no. 3 (2024): 2302876.

[13] C. A. F. Nason and Y. Xu, “Pre-Intercalation: A Valuable Approach for the Improvement of Post-Lithium Battery Materials,” eScience 4, no. 2 (2024): 100183.

[14] Z. Lu, S. Hao, Z. Wang, H. Kim, and C. Wolverton, “Phase Stability of Li-Rich Layered Cathodes: Insight Into the Debate Over Solid Solutions Vs Phase Separation,” Chemistry of Materials 36, no. 13 (2024): 6381–6391.

[15] J. Gan, Z. Wu, C. Zheng, et al., “Degradation, Intrinsic Microstrains and Phase Structure Engineering in Lithium-Rich Oxide Cathode Materials,” ACS Energy Letters 9, no. 12 (2024): 6153–6169.

[16] M. M. Thackeray, S.-H. Kang, C. S. Johnson, J. T. Vaughey, R. Benedek, and S. A. Hackney, “Li₂MnO₃-Stabilized LiMO₂ (M = Mn, Ni, Co) Electrodes for Lithium-Ion Batteries,” Journal of Materials Chemistry 17, no. 30 (2007): 3112–3125.

[17] M. Freire, N. V. Kosova, C. Jordy, et al., “A New Active Li-Mn-O Compound for High Energy Density Li-Ion Batteries,” Nature Materials 15, no. 2 (2016): 173–177.

[18] J. Wang, X. He, E. Paillard, N. Laszczynski, J. Li, and S. Passerini, “Lithium- and Manganese-Rich Oxide Cathode Materials for High-Energy Lithium Ion Batteries,” Advanced Energy Materials 6, no. 21 (2016): 1600906.

[19] Y. Zhang, X. Shi, S. Zheng, et al., “Alternate Heterogeneous Superlattice Control of Lattice Strain to Stabilize Li-Rich Cathode,” Energy & Environmental Science 16, no. 11 (2023): 5043–5051.

[20] Y. Yang, C. Gao, T. Luo, et al., “Unlocking the Potential of Li-Rich Mn-Based Oxides for High-Rate Rechargeable Lithium-Ion Batteries,” Advanced Materials 35, no. 52 (2023): 2307138.

[21] G. Assat and J.-M. Tarascon, “Fundamental Understanding and Practical Challenges of Anionic Redox Activity in Li-Ion Batteries,” Nature Energy 3, no. 5 (2018): 373–386.

[22] D.-H. Seo, J. Lee, A. Urban, R. Malik, S. Kang, and G. Ceder, “The Structural and Chemical Origin of the Oxygen Redox Activity in Layered and Cation-Disordered Li-Excess Cathode Materials,” Nature Chemistry 8, no. 7 (2016): 692–697.

[23] C. Zhan, Z. Yao, J. Lu, et al., “Enabling the High Capacity of Lithium-Rich Anti-Fluorite Lithium Iron Oxide by Simultaneous Anionic and Cationic Redox,” Nature Energy 2, no. 12 (2017): 963–971.

[24] W. Zhong, Z. Zeng, S. Cheng, and J. Xie, “Advancements in Prelithiation Technology: Transforming Batteries From Li-Shortage to Li-Rich Systems,” Advanced Functional Materials 34, no. 2 (2024): 2307860.

[25] X. Gao, B. Li, G. Rousse, et al., “Achieving High-Voltage Stability in Li-Rich Ni-Rich Oxides With Local W/Ni(Li) Superstructure,” Advanced Energy Materials 15, no. 3 (2024): 2402793.

[26] W. J. Kong, C. Z. Zhao, S. Sun, et al., “From Liquid to Solid-State Batteries: Li-Rich Mn-Based Layered Oxides as Emerging Cathodes With High Energy Density,” Advanced Materials 36, no. 14 (2024): 2310738.

[27] H. Ji, J. Wu, Z. Cai, et al., “Ultrahigh Power and Energy Density in Partially Ordered Lithium-Ion Cathode Materials,” Nature Energy 5, no. 3 (2020): 213–221.

[28] J. Lee, J. K. Papp, R. J. Clément, et al., “Mitigating Oxygen Loss to Improve the Cycling Performance of High Capacity Cation-Disordered Cathode Materials,” Nature Communications 8, no. 1 (2017): 981.

[29] D. Luo, H. Zhu, Y. Xia, et al., “A Li-Rich Layered Oxide Cathode With Negligible Voltage Decay,” Nature Energy 8, no. 10 (2023): 1078–1087.

[30] C. Shen, L. Hu, Q. Duan, et al., “Understanding Lattice Oxygen Redox Behavior in Lithium-Rich Manganese-Based Layered Oxides for Lithium-Ion and Lithium-Metal Batteries From Reaction Mechanisms to Regulation Strategies,” Advanced Energy Materials 13, no. 48 (2023): 2302957.

[31] Y. Yu, J. Zhang, R. Gao, et al., “Triggering Seversible Anion Sedox Chemistry in O3-Type Cathodes by Tuning Na/Mn Anti-Site Defects,” Energy & Environmental Science 16, no. 2 (2023): 584–597.

[32] Y. Jin, Z. Zhao, P. G. Ren, et al., “Recent Advances in Oxygen Redox Activity of Lithium-Rich Manganese-Based Layered Oxides Cathode Materials: Mechanism, Challenges and Strategies,” Advanced Energy Materials 14 (2024): 2402061.

[33] J.-J. Marie, R. A. House, G. J. Rees, et al., “Trapped O₂ and the Origin of Voltage Fade in Layered Li-Rich Cathodes,” Nature Materials 23 (2024): 818–825.

[34] C. Yan, Q. Shao, Y. Yang, et al., “Oxygen Release Suppression and Electronic Conductivity Enhancement for High Performance Li- and Mn-Rich Layered Oxides Cathodes by Chalcogenide Redox Couple and Oxygen Vacancy Generations,” Advanced Functional Materials 34, no. 19 (2024): 2310873.

[35] H. Park, H. Park, K. Song, et al., “In Situ Multiscale Probing of the Synthesis of a Ni-Rich Layered Oxide Cathode Reveals Reaction Heterogeneity Driven by Competing Kinetic Pathways,” Nature Chemistry 14, no. 6 (2022): 614–622.

[36] H.-Y. Jang, D. Eum, J. Cho, et al., “Structurally Robust Lithium-Rich Layered Oxides for High-Energy and Long-Lasting Cathodes,” Nature Communications 15, no. 1 (2024): 1288.

[37] L. Giordano, P. Karayaylali, Y. Yu, et al., “Chemical Reactivity Descriptor for the Oxide-Electrolyte Interface in Li-Ion Batteries,” Journal of Physical Chemistry Letters 8, no. 16 (2017): 3881–3887.

[38] R. Hausbrand, “Electronic Energy Levels at Li-Ion Cathode-Liquid Electrolyte Interfaces: Concepts, Experimental Insights, and Perspectives,” Journal of Chemical Physics 152, no. 18 (2020): 180902.

[39] L. An, J. Swallow, P. Cong, et al., “Distinguishing Bulk Redox From Near-Surface Degradation in Lithium Nickel Oxide Cathodes,” Energy & Environmental Science 17, no. 21 (2024): 8379–8391.

[40] S. Kang, D. Choi, H. Lee, B. Choi, and Y. M. Kang, “A Mechanistic Insight Into the Oxygen Redox of Li-Rich Layered Cathodes and Their Related Electronic/Atomic Behaviors Upon Cycling,” Advanced Materials 35, no. 43 (2023): 2211965.

[41] Y. Lai, H. Xie, P. Li, et al., “Ion-Migration Mechanism: An Overall Understanding of Anionic Redox Activity in Metal Oxide Cathodes of Li/Na-Ion Batteries,” Advanced Materials 34, no. 47 (2022): 2206039.

[42] H. Yu, H. Kim, Y. Wang, et al., “High-Energy ‘Composite’ Layered Manganese-Rich Cathode Materials via Controlling Li₂MnO₃ Phase Activation for Lithium-Ion Batteries,” Physical Chemistry Chemical Physics 14, no. 18 (2012): 6584–6595.

[43] R. Veena, J. Anbu Dinesh, S. Raman, P. Panigrahi, and N. Ganapathi Subramaniam, “Li and Mn-Rich Li₄Mn₅O₁₂-Li₂MnO₃ Composite Cathode for Next Generation Lithium-Ion Batteries,” Journal of Energy Storage 24 (2019): 100754.

[44] E. Wang, Y. Zhao, D. Xiao, et al., “Composite Nanostructure Construction on the Grain Surface of Li-Rich Layered Oxides,” Advanced Materials 32, no. 49 (2020): 1906070.

[45] R. J. Gummow, N. Sharma, R. Feng, G. Han, and Y. He, “High Performance Composite Lithium-Rich Nickel Manganese Oxide Cathodes for Lithium-Ion Batteries,” Journal of the Electrochemical Society 160, no. 10 (2013): A1856–A1862.

[46] S. Xu, Z. Chen, W. Zhao, et al., “Multi-Angle Tracking Synthetic Kinetics of Phase Evolution in Li-Rich Mn-Based Cathodes,” Energy & Environmental Science 17 (2024): 3807.

[47] H. Zhuo, H. Peng, B. Xiao, et al., “Atomic-Scale Revealing the Structure Distribution Between LiMO₂ and Li₂MnO₃ in Li-Rich and Mn-Based Oxide Cathode Materials,” Advanced Energy Materials 13, no. 14 (2023): 2203354.

[48] S. Jiao, Y. Sun, D. Shi, et al, “Structural Regulation-Induced Li-Electron Disentanglement for Stabilized Oxygen Redox of Li-Excess Disordered Rock-Salt Cathode Materials,” Energy & Environmental Science 17 (2024): 4977–4987.

[49] F. Ding, P. Ji, Z. Han, et al., “Tailoring Planar Strain for Robust Structural Stability in High-Entropy Layered Sodium Oxide Cathode Materials,” Nature Energy 9 (2024): 1529–1539.

[50] Z. Wang, E. Liu, L. Guo, et al., “Cycle Performance Improvement of Li-Rich Layered Cathode Material Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ by ZrO₂ Coating,” Surface and Coatings Technology 235 (2013): 570–576.

[51] Y. Liu, X. Fan, Z. Zhang, et al., “Enhanced Electrochemical Performance of Li-Rich Layered Cathode Materials by Combined Cr Doping and LiAlO₂ Coating,” ACS Sustainable Chemistry & Engineering 7, no. 2 (2018): 2225–2235.

[52] Y. Wei, J. Cheng, D. Li, et al., “A Structure Self-Healing Li-Rich Cathode Achieved by Lithium Supplement of Li-Rich LLZO Coating,” Advanced Functional Materials 33, no. 22 (2023): 2214775.

[53] C. Chen, T. Geng, C. Du, et al., “Oxygen Vacancies in SnO₂ Surface Coating to Enhance the Activation of Layered Li-Rich Li_1.2Mn_0.54-Ni_0.13Co_0.13O₂ Cathode Material for Li-Ion Batteries,” Journal of Power Sources 331 (2016): 91–99.

[54] J. Peng, Y. Li, Z. Chen, et al., “Phase Compatible NiFe₂O₄ Coating Tunes Oxygen Redox in Li-Rich Layered Oxide,” ACS Nano 15, no. 7 (2021): 11607–11618.

[55] Q.-Q. Qiu, Z. Shadike, Q.-C. Wang, et al., “Improving the Electrochemical Performance and Structural Stability of the LiNi_0.8-Co_0.15Al_0.05O₂ Cathode Material at High-Voltage Charging Through Ti Substitution,” ACS Applied Materials & Interfaces 11, no. 26 (2019): 23213–23221.

[56] 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.

[57] G. Yang, K. Pan, F. Lai, et al., “Integrated Co-Modification of PO₄³⁻ Polyanion Doping and Li₂TiO₃ Coating for Ni-Rich Layered LiNi_0.6-Co_0.2Mn_0.2O₂ Cathode Material of Lithium-Ion Batteries,” Chemical Engineering Journal 421 (2021): 129964.

[58] X. Gao, H. Zhang, S. Li, et al., “Local Electronic Structure Modulation Enables Fast-Charging Capability for Li-Rich Mn-Based Oxides Cathodes With Reversible Anionic Redox Activity,” Advanced Functional Materials 33, no. 43 (2023): 2304065.

[59] H. Wei, Y. Liu, Y. Luo, et al., “Regulation of Anion Redox Activity via Solid-Acid Modification for Highly Stable Li-Rich Mn-Based Layered Cathodes,” Advanced Functional Materials 34, no. 7 (2024): 2307583.

[60] W. Weppner and R. A. Huggins, “Determination of the Kinetic Parameters of Mixed-Conducting Electrodes and Application to the System Li₃Sb,” Journal of the Electrochemical Society 124, no. 10 (1977): 1569–1578.

[61] R. A. House, J.-J. Marie, M. A. Pérez-Osorio, G. J. Rees, E. Boivin, and P. G. Bruce, “The Role of O₂ in O-Redox Cathodes for Li-Ion Batteries,” Nature Energy 6, no. 8 (2021): 781–789.

[62] G. Assat, D. Foix, C. Delacourt, A. Iadecola, R. Dedryvère, and J. M. Tarascon, “Fundamental Interplay Between Anionic/Cationic Redox Governing the Kinetics and Thermodynamics of Lithium-Rich Cathodes,” Nature Communications 8, no. 1 (2017): 2219.

[63] M. Sathiya, G. Rousse, K. Ramesha, et al., “Reversible Anionic Redox Chemistry in High-Capacity Layered-Oxide Electrodes,” Nature Materials 12, no. 9 (2013): 827–835.

[64] K. Wang, J. Qiu, F. Hou, et al., “Unraveling the Role of Surficial Oxygen Vacancies in Stabilizing Li-Rich Layered Oxides,” Advanced Energy Materials 13, no. 32 (2023): 2301216.

[65] P. M. Csernica, S. S. Kalirai, W. E. Gent, et al., “Persistent and Partially Mobile Oxygen Vacancies in Li-Rich Layered Oxides,” Nature Energy 6, no. 6 (2021): 642–652.

[66] F. Wu, J. Dong, J. Zhao, et al., “Reversible Cationic-Anionic Redox in Disordered Rocksalt Cathodes Enabled by Fluorination-Induced Integrated Structure Design,” Journal of Energy Chemistry 82 (2023): 158–169.

[67] B. Qiu, M. Zhang, L. Wu, et al., “Gas-Solid Interfacial Modification of Oxygen Activity in Layered Oxide Cathodes for Lithium-Ion Batteries,” Nature Communications 7, no. 1 (2016): 12108.

[68] H. Kurata and C. Colliex, “Electron-Energy-Loss Core-Edge Structures in Manganese Oxides,” Physical Review B 48, no. 4 (1993): 2102–2108.

[69] T. Erichsen, B. Pfeiffer, V. Roddatis, and C. A. Volkert, “Tracking the Diffusion-Controlled Lithiation Reaction of LiMn₂O₄ by In Situ Tem,” ACS Applied Energy Materials 3, no. 6 (2020): 5405–5414.

[70] S. Sharifi-Asl, V. Yurkiv, A. Gutierrez, et al., “Revealing Grain-Boundary-Induced Degradation Mechanisms in Li-Rich Cathode Materials,” Nano Letters 20, no. 2 (2019): 1208–1217.

[71] Z. Wang, H. Xu, Z. Liu, et al., “A Recrystallization Approach to Repairing Spent LiFePO₄ Black Mass,” Journal of Materials Chemistry A 11, no. 16 (2023): 9057–9065.

RIGHTS & PERMISSIONS

2025 The Authors. Carbon Energy published by Wenzhou University and John Wiley & Sons Australia, Ltd.