Surface reconstruction via rapid solution quenching to enhance structural stability of lithium-rich layered cathodes

Abstract

Lithium-rich layered oxides are prospective materials for future-generation cathodes attributable to their high specific capacity. However, significant surface instability, particularly under high-voltage operating conditions, leads to substantial voltage decay and dramatic capacity degradation during long-term cycling, severely limiting their widespread application. In this study, we developed a universal brine quenching strategy to construct a stabilized composite surface structure for lithium-rich layered oxides. This structure comprises an inner surface layer with a Y-doped layered structure and an outermost layer featuring a disordered rock-salt structure. Doping in the layered structure strengthens the Y–O bonds, raises the energy barrier for oxygen evolution, and significantly increases the stability of the lithium-rich layered oxide surface, suppresses structural degradation during long-term cycling, and facilitates Li⁺ diffusion kinetics. The improved redox activity, combined with superior structural stability, contributes to an outstanding electrochemical performance. For instance, the Y-quenched Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ (LLO) cathode exhibited an improved discharge capacity of 283 mAh·g⁻¹ at 0.1 C and 223 mAh·g⁻¹ at 1 C, along with remarkable cyclic stability retaining 91.2% of its capacity after 300 cycles at 1 C, and a reduced voltage decay of 0.76 mV per cycle (compared to 1.16 mV per cycle for pristine LLO). This research provides valuable insights into the design and synthesis of high-energy-density lithium-rich layered oxides through a simple and cost-effective strategy.

Keywords

Li-rich layered oxides / brine quenching / surface structure / voltage decay / cycling stability

References

[1] Y. Tian, C. Lin, X.F. Meng, X. Yu, H.L. Li, and R. Xiong, Accelerated commercial battery electrode-level degradation diagnosis via only 11-point charging segments, eScience, 5(2025), No. 1, art. No. 100325.

[2] Ren LY, Liu B, Bao SX, et al.. Recovery of Li, Ni, Co and Mn from spent lithium-ion batteries assisted by organic acids: Process optimization and leaching mechanism. Int. J. Miner. Metall. Mater., 2024, 31(3): 518.

[3] Li Q, Wu YQ, Wang ZM, et al.. Carbon nanotubes coupled with metal ion diffusion layers stabilize oxide conversion reactions in high-voltage lithium-ion batteries. ACS Appl. Mater. Interfaces, 2020, 12(14): 16276.

[4] N. Guo, Z. Peng, W.J. Huo, et al., Stabilizing Zn metal anode through regulation of Zn ion transfer and interfacial behavior with a fast ion conductor protective layer, Small, 19(2023), No. 47, art. No. 2303963.

[5] S.C. Li, Y.Y. Liu, Y.G. Zhang, et al., Multi-functionalized full-interface integrated engineering towards highly reversible Li-rich Mn-based cathode, Energy Storage Mater., 66(2024), art. No. 103241.

[6] X.L. Chen, Z.L. Yu, X.J. Li, et al., Multifunctional siloxane additive enabling ultrahigh-nickel lithium battery with long cycle life at 30 and 60°C, Small, 21(2025), No. 7, art. No. 2409586.

[7] Meng FB, Xiong XY, Tan L, Yuan B, Hu RZ. Strategies for improving electrochemical reaction kinetics of cathode materials for subzero-temperature Li-ion batteries: A review. Energy Storage Mater., 2022, 44: 390.

[8] Fu BY, Moździerz M, Kulka A, Świerczek K. Recent progress in Ni-rich layered oxides and related cathode materials for Li-ion cells. Int. J. Miner. Metall. Mater., 2024, 31(11): 2345.

[9] W.S. Guo, W. Wei, H.W. Zhu, Y.J. Hu, H. Jiang, and C.Z. Li, In situ surface engineering enables high interface stability and rapid reaction kinetics for Ni-rich cathodes, eScience, 3(2023), No. 1, art. No. 100082.

[10] Y.L. Jin, Z.R. 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, Adv. Energy Mater., 14(2024), No. 40, art. No. 2470173.

[11] K. Zhou, Z.J. Zhang, B.W. Cao, et al., Aluminum sulfate surface treatment enabling long cycle life and low voltage decay lithium-rich manganese based oxide cathode, Nano Energy, 135(2025), art. No. 110639.

[12] C.L. Zheng, Y.Q. Wang, H.C. Mao, et al., Superexchange interaction regulates Ni/Mn spin states triggering Ni-t_2g/O-2p reductive coupling enabling stable lithium-rich cathode, Nat. Commun., 16(2025), No. 1, art. No. 3900.

[13] Yu Y, Li JL, Han GM, Yang Z, Zhong JJ, Kang FY. Optimize two-phase distribution of lithium-rich materials to stabilize structure and suppress voltage attenuation. Int. J. Miner. Metall. Mater., 2022, 29(12): 2201.

[14] Liu W, Li JX, Xu HY, Li J, Qiu XP. Stabilized cobalt-free lithium-rich cathode materials with an artificial lithium fluoride coating. Int. J. Miner. Metall. Mater., 2022, 29(5): 917.

[15] Li QY, Zhou D, Chu MH, et al.. A comprehensive understanding on the anionic redox chemistry of high-voltage cathode materials for high-energy-density lithium-ion batteries. Chem. Soc. Rev., 2025, 54(7): 3441.

[16] L. Rynearson, C. Antolini, C. Jayawardana, M. Yeddala, D. Hayes, and B.L. Lucht, Speciation of transition metal dissolution in electrolyte from common cathode materials, Angew. Chem. Int. Ed., 63(2024), No. 5, art. No. e202317109.

[17] McColl K, Coles SW, Zarabadi-Poor P, Morgan BJ, Islam MS. Phase segregation and nanoconfined fluid O₂ in a lithium-rich oxide cathode. Nat. Mater., 2024, 23(6): 826.

[18] Chen WX, Muhtar D, Li KL, et al.. Regulating cation disorder triggered-electronic reshuffling for sustainable conventional layered oxide cathodes. Chem. Mater., 2024, 36(3): 1249.

[19] S.L. Cui, M.Y. Gao, G.R. Li, and X.P. Gao, Insights into Li-rich Mn-based cathode materials with high capacity: From dimension to lattice to atom, Adv. Energy Mater., 12(2022), No. 4, art. No. 2003885.

[20] X.T. Zhu, X.J. Xie, J. Lin, et al., Tailoring redox couples of Lirich Mn-based cathode materials by in-situ surface reconstruction for high-performance lithium-ion batteries, Nano Energy, 134(2025), art. No. 110588.

[21] Y.L. Yang, C. Gao, T. Luo, et al., Unlocking the potential of Lirich Mn-based oxides for high-rate rechargeable lithium-ion batteries, Adv. Mater., 35(2023), No. 52, art. No. 2307138.

[22] S. Sun, C.Z. Zhao, G.Y. Liu, et al., Boosting anionic redox reactions of Li-rich cathodes through lattice oxygen and Li-ion kinetics modulation in working all-solid-state batteries, Adv. Mater., 37(2025), No. 6, art. No. 2414195.

[23] Y.L. Yang, J.F. Cai, Y.X. Zuo, et al., Enhancing the stability of Li-Rich Mn-based oxide cathodes through surface high-entropy strategy, Energy Storage Mater., 71(2024), art. No. 103587.

[24] Qiu SL, Fang TT, Zhu Y, et al.. Li_1.2Mn_0.6Ni_0.2O₂ with 3D porous rod-like hierarchical micro/nanostructure for high-performance cathode material. J. Alloys Compd., 2019, 790: 863.

[25] T. Zeng, M.L. Yang, F.C. Sun, et al., Interface engineering via constructing enhanced ligand enables highly stable Li-rich layered oxide cathode, Adv. Funct. Mater., 34(2024), No. 30, art. No. 2314528.

[26] G. Sun, C.T. Zhao, F.D. Yu, et al., In-situ surface chemical and structural self-reconstruction strategy enables high performance of Li-rich cathode, Nano Energy, 79(2021), art. No. 105459.

[27] L.L. Song, H.Y. Liang, S.Q. Li, B. Qiu, and Z.P. Liu, Challenges and strategies on high-manganese Li-rich layered oxide cathodes for ultrahigh-energy-density batteries, Acta Phys. Chim. Sin., 41(2025), No. 8, art. No. 100085.

[28] Wang ER, Yue J, Chu HL, et al.. Exploring a phase-compatible surface engineering for enhancing the structural stability in Li-rich layered oxides. J. Mater. Sci. Technol., 2026, 250: 165.

[29] Wang DH, Wang WL, Li KH, et al.. Low-temperature tolerant lithium-rich manganese-based cathode enabled by facile SnO₂ decoration. J. Mater. Chem. A, 2024, 12(24): 14467.

[30] E.R. Wang, Y. Zhao, D.D. Xiao, et al., Composite nanostructure construction on the grain surface of Li-rich layered oxides, Adv. Mater., 32(2020), No. 49, art. No. 1906070.

[31] Q.T. Jiang, X.F. Li, Y.C. Hao, et al., Oxygen-vacancy-assisted dual functional surface coatings suppressing irreversible phase transition of Li-rich layered oxide cathodes, Adv. Funct. Mater., 35(2025), No. 2, art. No. 2400670.

[32] X.P. Cai, S.Y. Li, J.F. Zhou, J.W. Zhang, N.S. Zhang, and X.L. Cui, Mitigating chain degradation of lithium-rich manganese-based cathode material by surface engineering, Energy Storage Mater., 71(2024), art. No. 103624.

[33] J.X. Meng, L.S. Xu, Q.X. Ma, et al., Modulating crystal and interfacial properties by W-gradient doping for highly stable and long life Li-rich layered cathodes, Adv. Funct. Mater., 32(2022), No. 19, art. No. 2113013.

[34] Liu ZP, Liu S, Yang L, et al.. Feasibility to improve the stability of lithium-rich layered oxides by surface doping. ACS Appl. Mater. Interfaces, 2022, 14(16): 18353.

[35] Li SW, Yang L, Liu ZP, et al.. Surface Al-doping for compromise between facilitating oxygen redox and enhancing structural stability of Li-rich layered oxide. Energy Storage Mater., 2023, 55: 356.

[36] T.H. Wu, X. Zhang, Y.Q. Li, et al., Quantitative identification of dopant occupation in Li-rich cathodes, Adv. Mater., 37(2025), No. 3, art. No. 2408543.

[37] Li JX, Xu HY, Li J, et al.. Construction of inorganic-rich cathode electrolyte interphase on Co-free cathodes. ACS Appl. Mater. Interfaces, 2023, 15(22): 26627.

[38] He HL, Dai XY, Wu FZ, et al.. Enhancing lithium-rich manganese cathodes: Structural optimization and defect engineering via innovative thermal treatment for improved electrochemical durability and efficiency. Ceram. Int., 2024, 50(20): 38792.

[39] Z. Su, S.N. Li, L. Ma, et al., Quenching-induced defects liberate the latent reversible capacity of lithium titanate anode, Adv. Mater., 35(2023), No. 5, art. No. 2208573.

[40] Yu YM, Liu JJ, Qi R, et al.. Interface-reconstruction forming bifunctional (Li_xTM_1−x)O rock-salt shell for enhanced cyclability in Li-rich layered oxide. Chin. J. Struct. Chem., 2020, 39(8): 1363

[41] Liu BS, Cheng K, Nie SC, et al.. Ice-water quenching induced Ti³⁺ self-doped TiO₂ with surface lattice distortion and the increased photocatalytic activity. J. Phys. Chem. C, 2017, 121(36): 19836.

[42] Li J, Zhang YJ, Guo X, et al.. Multifunctional surface-integrated structures enabling layered oxide cathodes with stable high-voltage cycling. ACS Energy Lett., 2024, 9(9): 4339.

[43] Yu WH, Wang YY, Wu AM, et al.. Suppress oxygen evolution of lithium-rich manganese-based cathode materials via an integrated strategy. Green Energy Environ., 2024, 9(1): 138.

[44] Zeng LC, Liang HY, Wang YQ, et al.. Quenching-induced lattice modifications endowing Li-rich layered cathodes with ultralow voltage decay and long life. Energy Environ. Sci., 2025, 18(1): 284.

[45] Kang SW, Wei XB, Chu YQ, et al.. Simultaneous dual modification of Li-rich Mn-based cathode in restraining oxygen release and structure distortion. J. Mater. Chem. A, 2024, 12(16): 9584.

[46] Jiang YS, Yu FD, Que LF, et al.. Revealing the thermodynamics and kinetics of in-plane disordered Li₂MnO₃ structure in Li-rich cathodes. ACS Energy Lett., 2021, 6(11): 3836.

[47] Toby BH, Von Dreele RB. GSAS-II: The genesis of a modern open-source all purpose crystallography software package. J. Appl. Crystallogr., 2013, 46(2): 544.

[48] Liu SY, Zhou YH, Zhang YB, et al.. Surface yttrium-doping induced by element segregation to suppress oxygen release in Li-rich layered oxide cathodes. Tungsten, 2022, 4(4): 336.

[49] G. Ko, S. Jeong, S. Park, et al., Doping strategies for enhancing the performance of lithium nickel manganese cobalt oxide cathode materials in lithium-ion batteries, Energy Storage Mater., 60(2023), art. No. 102840.

[50] Zhang C, Shen X, Li XY, et al.. Quenching-etched surface spinel to passivate layered cathode materials from structural degradation at high potentials. Chem. Mater., 2023, 35(17): 6692.

[51] Lu SQ, Zhang QH, Meng FQ, et al.. Surface lattice modulation through chemical delithiation toward a stable nickel-rich layered oxide cathode. J. Am. Chem. Soc., 2023, 145(13): 7397.

[52] H.B. Sun, Z.J. Yang, R. Ghosh, et al., Thermal processing to modulate surface chemistry and bulk charge distribution in nickel-rich layered lithium positive electrodes, Nat. Commun., 16(2025), No. 1, art. No. 1478.

[53] D. Luo, H.X. Xie, F.L. Tan, et al., Scalable nitrate treatment for constructing integrated surface structures to mitigate capacity fading and voltage decay of Li-rich layered oxides, Angew. Chem. Int. Ed., 61(2022), No. 27, art. No. e202203698.

[54] K. Wang, J.M. Qiu, F.C. Hou, et al., Unraveling the role of surficial oxygen vacancies in stabilizing Li-rich layered oxides, Adv. Energy Mater., 13(2023), No. 32, art. No. 2301216.

[55] W.Q. Du, Y.Q. Zheng, X.Y. Liu, et al., Oxygen-enriched vacancy spinel MFe₂O₄/carbon (M = Ni, Mn, Co) derived from metal-organic frameworks toward boosting lithium storage, Chem. Eng. J., 451(2023), art. No. 138626.

[56] X.H. Tan, Y.X. Zhang, S.Y. Xu, et al., High-entropy surface complex stabilized LiCoO₂ cathode, Adv. Energy Mater., 13(2023), No. 24, art. No. 2300147.

[57] J.J. Fang, K.C. Xie, Y.L. Song, et al., Break the capacity limit of Li₄Ti₅O₁₂ anodes through oxygen vacancy engineering, Chin. J. Struct. Chem., 44(2025), No. 2, art. No. 100504.

[58] X. Sun, C.L. Qin, B.Y. Zhao, et al., A cation and anion dual-doping strategy in novel Li-rich Mn-based cathode materials for high-performance Li metal batteries, Energy Storage Mater., 70(2024), art. No. 103559.

[59] Yang J, Tao YH, Zhao CJ, Cai Y, Xiao P, Shi MJ. Tailorable dual-redox polymer with molecular flexibility for enhanced electrochemical desalination and water purification. Environ. Sci. Technol., 2025, 59(22): 10980.

[60] Zhao Y, Wang B, Shi MJ, An SB, Zhao LP, Yan C. Mg-intercalation engineering of MnO₂ electrode for high-performance aqueous magnesium-ion batteries. Int. J. Miner. Metall. Mater., 2022, 29(11): 1954.

[61] Shi MJ, Zhu HT, Chen C, Jiang JT, Zhao LP, Yan C. Synergistically coupling of graphene quantum dots with Zn-in-tercalated MnO₂ cathode for high-performance aqueous Zn-ion batteries. Int. J. Miner. Metall. Mater., 2023, 30(1): 25.

[62] Y.Y. Liu, C.Y. Zhang, L. Lin, et al., Intrinsic highly conductive and mechanically robust Li-rich cathode materials enabled by microstructure engineering for enhanced electrochemical properties, Adv. Funct. Mater., 34(2023), No. 6, Art. No. 2308494.

[63] Sathiya M, Rousse G, Ramesha K, et al.. Reversible anionic redox chemistry in high-capacity layered-oxide electrodes. Nat. Mater., 2013, 12(9): 827.

[64] S.J. Qiu, L.D. Duan, E.R. Wang, et al., Countering voltage fade and capacity decay of Li-rich layered oxides endowed by a hydridoaluminate additive, J. Alloys Compd., 1022(2025), art. No. 179885.

[65] D. Lu, Y.F. Chen, W.W. Sun, et al., Cathode electrolyte interface engineering by gradient fluorination for high-performance lithium rich cathode, Adv. Energy Mater., 13(2023), No. 34, art. No. 2301765.

[66] Q.T. Jiang, M. Li, J. Li, et al., LiF-rich cathode electrolyte interphases homogenizing Li⁺ fluxes toward stable interface in Li-rich Mn-based cathodes, Adv. Mater., 37(2025), No. 15, art. No. 2417620.

RIGHTS & PERMISSIONS

University of Science and Technology Beijing