Uncovering the Critical Role of Ni on Surface Lattice Stability in Anionic Redox Active Li_1.2Ni_0.2Mn_0.6O₂

Abstract

Anionic redox reaction (ARR) can provide extra capacity beyond transition metal (TM) redox in lithium-rich TM oxide cathodes. Practical ARR application is much hindered by the structure instability, particularly at the surface. Oxygen release has been widely accepted as the ringleader of surficial structure instability. However, the role of TM in surface stability has been much overlooked, not to mention its interplay with oxygen release. Herein, TM dissolution and oxygen release are comparatively investigated in Li_1.2Ni_0.2Mn_0.6O₂. Ni is verified to detach from the lattice counter-intuitively despite the overwhelming stoichiometry of Mn, facilitating subsequent oxygen release of the ARR process. Intriguingly, surface reorganization occurs following regulated Ni dissolution, enabling the stabilization of the surface and elimination of oxygen release in turn. Accordingly, a novel optimization strategy is proposed by adding a relaxation step at 4.50 V within the first cycle procedure. Battery performance can be effectively improved, with voltage decay suppressed from 3.44 mV/cycle to 1.60 mV/cycle, and cycle stability improved from 66.77% to 90.01% after 100 cycles. This work provides new perspectives for clarifying ARR surface instability and guidance for optimizing ARR performance.

Keywords

anionic redox reaction / oxygen release / surface reorganization / TM dissolution

References

[1] J. B. Goodenough, “Evolution of Strategies for Modern Rechargeable Batteries,” Accounts of Chemical Research 46, no. 5 (2013): 1053-1061.

[2] 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.

[3] X. Liu, G.-L. Xu, V. S. C. Kolluru, et al., “Origin and Regulation of Oxygen Redox Instability in High-Voltage Battery Cathodes,” Nature Energy 7, no. 9 (2022): 808-817.

[4] B. Li, Z. Zhuo, L. Zhang, et al., “Decoupling the Roles of Ni and Co in Anionic Redox Activity of Li-Rich NMC Cathodes,” Nature Materials 22, no. 11 (2023): 1370-1379.

[5] X. Wang, Q. Zhang, C. Zhao, et al., “Achieving a High-Performance Sodium-Ion Pouch Cell by Regulating Intergrowth Structures in a Layered Oxide Cathode With Anionic Redox,” Nature Energy 9, no. 2 (2024): 184-196.

[6] W. He, W. Guo, H. Wu, et al., “Challenges and Recent Advances in High Capacity Li-Rich Cathode Materials for High Energy Density Lithium-Ion Batteries,” Advanced Materials 33, no. 50 (2021): 2005937.

[7] X. Cao, H. Li, Y. Qiao, et al., “Reversible Anionic Redox Chemistry in Layered Li_4/7[□_1/7Mn_6/7]O₂ Enabled By Stable Li-O-Vacancy Configuration,” Joule 6, no. 6 (2022): 1290-1303.

[8] H. Ren, Y. Li, Q. Ni, Y. Bai, H. Zhao, and C. Wu, “Unraveling Anionic Redox for Sodium Layered Oxide Cathodes: Breakthroughs and Perspectives,” Advanced Materials 34, no. 8 (2022): 202106171.

[9] K. Wang, H. Zhuo, J. Wang, F. Poon, X. Sun, and B. Xiao, “Recent Advances in Mn-Rich Layered Materials for Sodium-Ion Batteries,” Advanced Functional Materials 33, no. 13 (2023): 2212607.

[10] E. Hu, Q. Li, X. Wang, et al., “Oxygen-Redox Reactions in LiCoO₂ Cathode Without O-O Bonding During Charge-Discharge,” Joule. 5, no. 3 (2021): 720-736.

[11] X. Li, J. Xu, H. Li, H. Zhu, S. Guo, and H. Zhou, “Synergetic Anion-Cation Redox Ensures a Highly Stable Layered Cathode for Sodium-Ion Batteries,” Advanced Science 9, no. 16 (2022): 2105280.

[12] W. Zuo, M. Luo, X. Liu, et al., “Li-Rich Cathodes for Rechargeable Li-Based Batteries: Reaction Mechanisms and Advanced Characterization Techniques,” Energy & Environmental Science 13, no. 12 (2020): 4450-4497.

[13] M. Ben Yahia, J. Vergnet, M. Saubanère, and M.-L. Doublet, “Unified Picture of Anionic Redox in Li/Na-Ion Batteries,” Nature Materials 18, no. 5 (2019): 496-502.

[14] W. Yang, “Another View of Oxygen in Cathodes for High Energy Batteries,” Joule 6, no. 5 (2022): 946-949.

[15] L. Zeng, H. Liang, B. Qiu, et al., “Voltage Decay of Li-Rich Layered Oxides: Mechanism, Modification Strategies, and Perspectives,” Advanced Functional Materials 33, no. 25 (2023): 202213260.

[16] D. Eum, B. Kim, S. J. Kim, et al., “Voltage Decay and Redox Asymmetry Mitigation by Reversible Cation Migration in Lithium-Rich Layered Oxide Electrodes,” Nature Materials 19, no. 4 (2020): 419-427.

[17] W. Zheng, G. Liang, S. Zhang, K. Davey, and Z. Guo, “Understanding Voltage Hysteresis and Decay During Anionic Redox Reaction in Layered Transition Metal Oxide Cathodes: A Critical Review,” Nano Research 16, no. 3 (2022): 3766-3780.

[18] Y. Li, S. Zheng, J. Xie, et al., “Single O Hole Enables High Cycling Performance by Removing Thermodynamic and Kinetic Limitations,” ACS Energy Letters 9, no. 10 (2024): 4864-4874.

[19] S. Sharifi-Asl, J. Lu, K. Amine, and R. Shahbazian-Yassar, “Oxygen Release Degradation in Li-Ion Battery Cathode Materials: Mechanisms and Mitigating Approaches,” Advanced Energy Materials 9, no. 22 (2019): 1900551.

[20] K. Wu, P. Ran, S. Wang, et al., “Confining Bulk Molecular O₂ by Inhibiting Charge Transfer on Surface Anions Toward Stable Redox Electrochemistry in Layered Oxide Cathodes,” Nano Energy 113 (2023): 108602.

[21] X. Xia, T. Liu, C. Cheng, et al., “Suppressing the Dynamic Oxygen Evolution of Sodium Layered Cathodes Through Synergistic Surface Dielectric Polarization and Bulk Site-Selective Co-Doping,” Advanced Materials 35, no. 8 (2023): 2209556.

[22] C. Yin, X. Wen, L. Wan, et al., “Surface Reinforcement Doping to Suppress Oxygen Release of Li-Rich Layered Oxides,” Journal of Power Sources 503 (2021): 230048.

[23] P. Yan, J. Zheng, Z.-K. Tang, et al., “Injection of Oxygen Vacancies in the Bulk Lattice of Layered Cathodes,” Nature Nanotechnology 14, no. 6 (2019): 602-608.

[24] S. Y. Kim, C. S. Park, S. Hosseini, J. Lampert, Y. J. Kim, and L. F. Nazar, “Inhibiting Oxygen Release From Li-Rich, Mn-Rich Layered Oxides at the Surface With a Solution Processable Oxygen Scavenger Polymer,” Advanced Energy Materials 11, no. 30 (2021): 2100552.

[25] J. Sun, C. Sheng, X. Cao, et al., “Restraining Oxygen Release and Suppressing Structure Distortion in Single-Crystal Li-Rich Layered Cathode Materials,” Advanced Functional Materials 32, no. 10 (2022): 2110295.

[26] W. Yang, “Oxygen Release and Oxygen Redox,” Nature Energy 3, no. 8 (2018): 619-620.

[27] B. Kim and K. Kang, “Stabilizing Oxygen Redox Chemistry for the Realization of High-Capacity Batteries,” Nature Sustainability 5, no. 8 (2022): 647-648.

[28] X. Zhang, J. Zhao, G.-H. Lee, et al., “Bulk Oxygen Stabilization via Electrode-Electrolyte Interphase Tailored Surface Activities of Li-Rich Cathodes,” Advanced Energy Materials 13, no. 2 (2023): 2202929.

[29] L.-X. Ma, T.-D. Chen, C.-X. Hai, et al., “Surface Engineering of Li- and Mn-Rich Layered Oxides for Superior Li-Ion Battery,” Tungsten 6, no. 1 (2022): 259-268.

[30] D. He, W. Tong, J. Zhang, et al., “Structural Insights Into Lithium-Deficient Type Li-Rich Layered Oxide for High-Performance Cathode,” Chinese Journal of Structural Chemistry 42, no. 5 (2023): 100060.

[31] Y. Pan, Y. Zhu, Y. Li, et al., “Homonuclear Transition-Metal Dimers Embedded Monolayer C₂N as Promising Anchoring and Electrocatalytic Materials for Lithium-Sulfur Battery: First-Principles Calculations,” Applied Surface Science 610 (2023): 155507.

[32] A. Manthiram, “A Reflection on Lithium-Ion Battery Cathode Chemistry,” Nature Communications 11, no. 1 (2020): 1550.

[33] H. Pan, S. Jiao, Z. Xue, et al., “The Roles of Ni and Mn in the Thermal Stability of Lithium-Rich Manganese-Rich Oxide Cathode,” Advanced Energy Materials 13, no. 15 (2023): 2203989.

[34] G. Zhou, X. Sun, Q.-H. Li, et al., “Mn Ion Dissolution Mechanism for Lithium-Ion Battery With LiMn₂O₄ Cathode: In Situ Ultraviolet-Visible Spectroscopy and Ab Initio Molecular Dynamics Simulations,” Journal of Physical Chemistry Letters 11, no. 8 (2020): 3051-3057.

[35] J. Li, G. Liang, W. Zheng, et al., “Addressing Cation Mixing in Layered Structured Cathodes for Lithium-Ion Batteries: A Critical Review,” Nano Materials Science 5, no. 4 (2023): 404-420.

[36] C. Zhan, T. Wu, J. Lu, and K. Amine, “Dissolution, Migration, and Deposition of Transition Metal Ions in Li-Ion Batteries Exemplified by Mn-Based Cathodes—A Critical Review,” Energy & Environmental Science 11, no. 2 (2018): 243-257.

[37] J. Yang, P. Li, F. Zhong, et al., “Suppressing Voltage Fading of Li-Rich Oxide Cathode via Building a Well-Protected and Partially-Protonated Surface by Polyacrylic Acid Binder for Cycle-Stable Li-Ion Batteries,” Advanced Energy Materials 10, no. 15 (2020): 1904264.

[38] Y. Li, W. Li, R. Shimizu, et al., “Elucidating the Effect of Borate Additive in High-Voltage Electrolyte for Li-Rich Layered Oxide Materials,” Advanced Energy Materials 12, no. 11 (2022): 2103033.

[39] J. Liu, Z. Wu, M. Yu, et al., “Building Homogenous Li₂TiO₃ Coating Layer on Primary Particles to Stabilize Li-Rich Mn-Based Cathode Materials,” Small 18, no. 10 (2022): 2106337.

[40] B. Cao, T. Li, W. Zhao, et al., “Correlating Rate-Dependent Transition Metal Dissolution Between Structure Degradation in Li-Rich Layered Oxides,” Small 19, no. 42 (2023): 2301834.

[41] T. Liu, A. Dai, J. Lu, et al., “Correlation Between Manganese Dissolution and Dynamic Phase Stability in Spinel-Based Lithium-Ion Battery,” Nature Communications 10, no. 1 (2019): 4721.

[42] Y. Zhao, J. Liu, S. Wang, et al., “Surface Structural Transition Induced by Gradient Polyanion-Doping in Li-Rich Layered Oxides: Implications for Enhanced Electrochemical Performance,” Advanced Functional Materials 26, no. 26 (2016): 4760-4767.

[43] K. Zhang, J. Qi, J. Song, et al., “Sulfuration of Li-Rich Mn-Based Cathode Materials for Multianionic Redox and Stabilized Coordination Environment,” Advanced Materials 34, no. 11 (2022): 2109564.

[44] 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.

[45] 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 (2020): 1208-1217.

[46] X. He, J. Wu, Z. Zhu, et al., “Chemical and Structural Evolutions of Li-Mn-Rich Layered Electrodes at Different Current Densities,” Energy & Environmental Science 15, no. 10 (2022): 4137-4147.

[47] Z. Xu, X. Guo, J. Wang, et al., “Restraining the Octahedron Collapse in Lithium and Manganese Rich NCM Cathode Toward Suppressing Structure Transformation,” Advanced Energy Materials 12, no. 35 (2022): 2201323.

[48] 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.

[49] S. Liu, B. Wang, X. Zhang, S. Zhao, Z. Zhang, and H. Yu, “Reviving the Lithium-Manganese-Based Layered Oxide Cathodes for Lithium-Ion Batteries,” Matter 4, no. 5 (2021): 1511-1527.

[50] X. Li, Q. Gu, B. Qiu, et al., “Rational Design of Thermally Stable Polymorphic Layered Cathode Materials for Next Generation Lithium Rechargeable Batteries,” Materials Today 61 (2022): 91-103.

[51] M. Gu, I. Belharouak, A. Genc, et al., “Conflicting Roles of Nickel in Controlling Cathode Performance in Lithium Ion Batteries,” Nano Letters 12, no. 10 (2012): 5186-5191.

[52] J. Zheng, M. Gu, A. Genc, et al., “Mitigating Voltage Fade in Cathode Materials by Improving the Atomic Level Uniformity of Elemental Distribution,” Nano Letters 14, no. 5 (2014): 2628-2635.

[53] T. Mizokawa, Y. Wakisaka, T. Sudayama, et al., “Role of Oxygen Holes in Li_xCoO₂ Revealed By Soft X-Ray Spectroscopy,” Physical Review Letters 111, no. 5 (2013): 056404.

[54] K. Luo, M. R. Roberts, R. Hao, et al., “Charge-Compensation in 3d-Transition-Metal-Oxide Intercalation Cathodes Through the Generation of Localized Electron Holes on Oxygen,” Nature Chemistry 8, no. 7 (2016): 684-691.

[55] W. Yang and T. P. Devereaux, “Anionic and Cationic Redox and Interfaces in Batteries: Advances From Soft X-Ray Absorption Spectroscopy to Resonant Inelastic Scattering,” Journal of Power Sources 389 (2018): 188-197.

[56] Z. Zhuo, K. Dai, J. Wu, et al., “Distinct Oxygen Redox Activities in Li₂MO₃ (M = Mn, Ru, Ir),” ACS Energy Letters 6, no. 10 (2021): 3417-3424.

[57] R. A. House, G. J. Rees, M. A. Pérez-Osorio, et al., “First-Cycle Voltage Hysteresis in Li-Rich 3d Cathodes Associated With Molecular O₂ Trapped in the Bulk,” Nature Energy 5, no. 10 (2020): 777-785.

[58] M. Merz, B. Ying, P. Nagel, S. Schuppler, and K. Kleiner, “Reversible and Irreversible Redox Processes in Li-Rich Layered Oxides,” Chemistry of Materials 33, no. 24 (2021): 9534-9545.

[59] X.-D. Zhang, J.-L. Shi, J.-Y. Liang, et al., “Suppressing Surface Lattice Oxygen Release of Li-Rich Cathode Materials via Heterostructured Spinel Li₄Mn₅O₁₂ Coating,” Advanced Materials 30, no. 29 (2018): 1801751.

[60] X. Gou, Z. Hao, Z. Hao, et al., “In Situ Surface Self-Reconstruction Strategies in Li-Rich Mn-Based Layered Cathodes for Energy-Dense Li-Ion Batteries,” Advanced Functional Materials 32, no. 18 (2022): 2112088.

[61] H. Zhang, X. Li, W. Wang, et al., “Ambient Pressure Mapping of Resonant Auger Spectroscopy at BL02B01 at the Shanghai Synchrotron Radiation Facility,” Review of Scientific Instruments 91, no. 12 (2020): 123108.

[62] G. Assat, A. Iadecola, D. Foix, R. Dedryvère, and J.-M. Tarascon, “Direct Quantification of Anionic Redox Over Long Cycling of Li-Rich NMC via Hard X-Ray Photoemission Spectroscopy,” ACS Energy Letters 3, no. 11 (2018): 2721-2728.

[63] Q. Li, Y. Wang, X. Wang, et al., “Investigations on the Fundamental Process of Cathode Electrolyte Interphase Formation and Evolution of High-Voltage Cathodes,” ACS Applied Materials & Interfaces 12, no. 2 (2020): 2319-2326.

[64] Q. Li, Q. Liang, H. Zhang, et al., “Unveiling the High-Valence Oxygen Degradation Across the Delithiated Cathode Surface,” Angewandte Chemie International Edition 62, no. 5 (2023): e202215131.

[65] P. Yan, A. Nie, J. Zheng, et al., “Evolution of Lattice Structure and Chemical Composition of the Surface Reconstruction Layer in Li_1.2Ni_0.2Mn_0.6O₂ Cathode Material for Lithium Ion Batteries,” Nano Letters 15, no. 1 (2015): 514-522.

[66] P. Yan, J. Zheng, J.-G. Zhang, and C. Wang, “Atomic Resolution Structural and Chemical Imaging Revealing the Sequential Migration of Ni, Co, and Mn Upon the Battery Cycling of Layered Cathode,” Nano Letters 17, no. 6 (2017): 3946-3951.

[67] H. Yu, Y.-G. So, Y. Ren, et al., “Temperature-Sensitive Structure Evolution of Lithium-Manganese-Rich Layered Oxides for Lithium-Ion Batteries,” Journal of the American Chemical Society 140, no. 45 (2018): 15279-15289.

[68] C. Cai, D. Zhang, Q. Zhang, et al., “Origin of Oxygen-Redox and Transition Metals Dissolution in Ni-Rich Li_xNi_0.8Co_0.1Mn_0.1O₂ Cathode,” Journal of Chemical Physics 158, no. 11 (2023): 114703.

[69] J. Liu, Z. Du, X. Wang, et al., “Anionic Redox Induced Anomalous Structural Transition in Ni-Rich Cathodes,” Energy & Environmental Science 14, no. 12 (2021): 6441-6454.

[70] Z. Liu, R. Liu, S. Xu, et al., “Achieving a Deeply Desodiated Stabilized Cathode Material by the High Entropy Strategy for Sodium-Ion Batteries,” Angewandte Chemie International Edition 63, no. 29 (2024): e202405620.

[71] Z. Ruff, C. Xu, and C. P. Grey, “Transition Metal Dissolution and Degradation in NMC811-Graphite Electrochemical Cells,” Journal of the Electrochemical Society 168, no. 6 (2021): 060518.

[72] D.-S. Ko, J.-H. Park, S. Park, et al., “Microstructural Visualization of Compositional Changes Induced by Transition Metal Dissolution in Ni-Rich Layered Cathode Materials by High-Resolution Particle Analysis,” Nano Energy 56 (2019): 434-442.

RIGHTS & PERMISSIONS

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