Improving the structure and cycling stability of Ni-rich cathodes by dual modification

Abstract

The irreversible phase transition and interface side reactions during the cycling process severely limit the large-scale application of nickel-rich layered oxides Li[Ni _xCo _yMn_1−x−y]O₂ (NCM, x>0.8). Herein, we have designed LiNi_0.8Co_0.1Mn_0.1O₂ cathodes modified by Nb/Al co-doping and LiNbO₃/LiAlO₂ composite coating. Detailed characterization reveals that Nb/Al co-doping can stabilize the crystal structure of the cathodes and expand the layer spacing of the layered lattice, thereby increasing the diffusion rate and reversibility of Li⁺. And the composite coatings can improve the electrochemical kinetic and inhibit the erosion of acidic substances by hindering direct contact between the cathodes and electrolyte. As a result, the Ni-rich cathodes with dual modification can still exhibit a higher capacity of 184.02 mA·h/g after 100 cycles with a capacity retention of up to 98.1%, and can still release a capacity of 161.6 mA·h/g at a high rate of 7C, meanwhile, it shows excellent thermal stability compared to bare NCM. This work provides a new perspective for enhancing electrochemical properties of cathodes through integrated strategies.

References

[1] Armand M, Tarascon J M. Building better batteries [J]. Nature, 2008, 451(7179): 652-657.

[2] Sari H M K, Li X-fei. Controllable cathode-electrolyte interface of Li[Ni_0.8Co_0.1Mn_0.1]O₂ for lithium ion batteries: A review [J]. Advanced Energy Materials, 2019, 9(39): 1901597.

[3] Zhang Z-a, Qu C-m, Jia M, et al.. Predispersed carbon black as conductive agent for LiFePO₄ cathodes [J]. Journal of Central South University, 2014, 21(7): 2604-2611.

[4] Xiao Z-w, Zhang Y-j, Hu G-rong. Effect of different carbon precursors on properties of LiFePO₄/C [J]. Journal of Central South University, 2015, 22(12): 4507-4514.

[5] Li Y-j, Li L, Su Q-y, et al.. Thermodynamic analysis of Li-Ni-Co-Mn-H₂O system and synthesis of LiNi_0.5Co_0.2Mn_0.3O₂ composite oxide via aqueous process [J]. Journal of Central South University, 2019, 26(10): 2668-2680.

[6] Wu F-x, Maier J, Yu Yan. Guidelines and trends for next-generation rechargeable lithium and lithium-ion batteries [J]. Chemical Society Reviews, 2020, 49(5): 1569-1614.

[7] Hou P Y, Zhang L Q, Gao X P. A high-energy, full concentration-gradient cathode material with excellent cycle and thermal stability for lithium ion batteries [J]. Journal of Materials Chemistry A, 2014, 2(40): 17130-17138.

[8] Chu B-b, Liu S-y, You L-z, et al.. Enhancing the cycling stability of Ni-rich LiNi_0.6Co_0.2Mn_0.2O₂ cathode at a high cutoff voltage with Ta doping [J]. ACS Sustainable Chemistry & Engineering, 2020, 8(8): 3082-3090.

[9] Wu F, Liu N, Chen L, et al.. Improving the reversibility of the H2-H3 phase transitions for layered Ni-rich oxide cathode towards retarded structural transition and enhanced cycle stability [J]. Nano Energy, 2019, 59: 50-57.

[10] Huang Y, Liu X, Yu R-z, et al.. Tellurium surface doping to enhance the structural stability and electrochemical performance of layered Ni-rich cathodes [J]. ACS Applied Materials & Interfaces, 2019, 11(43): 40022-40033.

[11] Qiu L, Xiang W, Tian W, et al.. Polyanion and cation co-doping stabilized Ni-rich Ni-Co-Al material as cathode with enhanced electrochemical performance for Li-ion battery [J]. Nano Energy, 2019, 63: 103818.

[12] Zhou P-f, Meng H-j, Zhang Z, et al.. Stable layered Ni-rich LiNi_0.9Co_0.07Al_0.03O₂ microspheres assembled with nanoparticles as high-performance cathode materials for lithium-ion batteries [J]. Journal of Materials Chemistry A, 2017, 5(6): 2724-2731.

[13] Zou L-f, Zhao W-g, Liu Z-y, et al.. Revealing cycling rate-dependent structure evolution in Ni-rich layered cathode materials [J]. ACS Energy Letters, 2018, 3(10): 2433-2440.

[14] Zhang C-x, Xu S, Han B, et al.. Towards rational design of high performance Ni-rich layered oxide cathodes: The interplay of borate-doping and excess lithium [J]. Journal of Power Sources, 2019, 431: 40-47.

[15] Yang H-p, Wu H-h, Ge M-y, et al.. Simultaneously dual modification of Ni-rich layered oxide cathode for high-energy lithium-ion batteries [J]. Advanced Functional Materials, 2019, 29(13): 1808825.

[16] Yan P-f, Zheng J-m, Liu J, et al.. Tailoring grain boundary structures and chemistry of Ni-rich layered cathodes for enhanced cycle stability of lithium-ion batteries [J]. Nature Energy, 2018, 3: 600-605.

[17] Sheng H, Meng X-h, Xiao D-d, et al.. An air-stable high-nickel cathode with reinforced electrochemical performance enabled by convertible amorphous Li₂CO₃ modification [J]. Advanced Materials, 2022, 34(12): e2108947.

[18] Huang X, Zhu W-c, Yao J-y, et al.. Suppressing structural degradation of Ni-rich cathode materials towards improved cycling stability enabled by a Li₂MnO₃ coating [J]. Journal of Materials Chemistry A, 2020, 8(34): 17429-17441.

[19] Yu H-f, Cao Y-q, Chen L, et al.. Surface enrichment and diffusion enabling gradient-doping and coating of Ni-rich cathode toward Li-ion batteries [J]. Nature Communications, 2021, 12(1): 4564.

[20] Hwang J Y, Myung S T, Yoon C S, et al.. Novel cathode materials for Na-ion batteries composed of spoke-like nanorods of Na[Ni_0.61Co_0.12Mn_0.27]O₂ assembled in spherical secondary particles [J]. Advanced Functional Materials, 2016, 26(44): 8083-8093.

[21] Zhao C, Wang C-w, Liu X, et al.. Suppressing strain propagation in ultrahigh-Ni cathodes during fast charging via epitaxial entropy-assisted coating [J]. Nature Energy, 2024, 9: 345-356.

[22] Liang L-w, Su M-s, Sun Z-f, et al.. High-entropy doping promising ultrahigh-Ni co-free single-crystalline cathode toward commercializable high-energy lithium-ion batteries [J]. Science Advances, 2024, 10(25): eado4472.

[23] Liu W, Li X-f, Xiong D-b, et al.. Significantly improving cycling performance of cathodes in lithium ion batteries: The effect of Al₂O₃ and LiAlO₂ coatings on LiNi_0.6Co_0.2Mn_0.2O₂ [J]. Nano Energy, 2018, 44: 111-120.

[24] Ban C-m, Li Z, Wu Z-c, et al.. Extremely durable high-rate capability of a LiNi_0.4Mn_0.4Co_0.2O₂ cathode enabled with single-walled carbon nanotubes [J]. Advanced Energy Materials, 2011, 1(1): 58-62.

[25] Su Y-f, Yang Y-q, Chen L, et al.. Improving the cycling stability of Ni-rich cathode materials by fabricating surface rock salt phase [J]. Electrochimica Acta, 2018, 292: 217-226.

[26] Schipper F, Bouzaglo H, Dixit M, et al.. From surface ZrO₂ coating to bulk Zr doping by high temperature annealing of nickel-rich lithiated oxides and their enhanced electrochemical performance in lithium ion batteries [J]. Advanced Energy Materials, 2018, 8(4): 1701682.

[27] Zhang C-x, Wei B, Jiang W-j, et al.. Insights into the enhanced structural and thermal stabilities of Nb-substituted lithium-rich layered oxide cathodes [J]. ACS Applied Materials & Interfaces, 2021, 13(38): 45619-45629.

[28] Shang G-z, Tang Y-w, Lai Y-q, et al.. Enhancing structural stability unto 4.5 V of Ni-rich cathodes by tungsten-doping for lithium storage [J]. Journal of Power Sources, 2019, 423: 246-254.

[29] Liu D, Liu S-y, Zhang C-c, et al.. Revealing the effect of Ti doping on significantly enhancing cyclic performance at a high cutoff voltage for Ni-rich LiNi_0.8Co_0.15Al_0.05O₂ cathode [J]. ACS Sustainable Chemistry & Engineering, 2019, 7(12): 10661-10669.

[30] Zhang C-x, Wei B, Wang M-y, et al.. Regulating oxygen covalent electron localization to enhance anionic redox reversibility of lithium-rich layered oxide cathodes [J]. Energy Storage Materials, 2022, 46: 512-522.

[31] Luo M, Zhang R, Gong Y-q, et al.. Effects of doping Al on the structure and electrochemical performances of Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ cathode materials [J]. Ionics, 2018, 24(4): 967-976.

[32] Ni L-s, Chen H-y, Gao J-q, et al.. Multiscale crystal field effect for high-performance ultrahigh-Ni layered cathode [J]. ACS Nano, 2023, 17(13): 12759-12773.

[33] Dong Q-y, Wu J-h, Wang Y-q, et al.. Bifunctional self-assembled molecular layer enables stable Ni-rich cathodes [J]. Energy Storage Materials, 2023, 63: 103054.

[34] Zou Y-g, Mao H-c, Meng X-h, et al.. Mitigating the kinetic hindrance of single-crystalline Ni-rich cathode via surface gradient penetration of tantalum [J]. Angewandte Chemie International Edition, 2021, 60(51): 26535-26539.

[35] Zhou Y, Zhang H-w, Wang Y-l, et al.. Relieving stress concentration through anion-cation codoping toward highly stable nickel-rich cathode [J]. ACS Nano, 2023, 17(20): 20621-20633.

[36] Wang Y-y, Liang Z-m, Liu Z-c, et al.. Synergy of epitaxial layer and bulk doping enables structural rigidity of cobalt-free ultrahigh-nickel oxide cathode for lithium-ion batteries [J]. Advanced Functional Materials, 2023, 33(52): 2308152.

[37] Ko D S, Park J H, Yu B Y, et al.. Degradation of high-nickel-layered oxide cathodes from surface to bulk: A comprehensive structural, chemical, and electrical analysis [J]. Advanced Energy Materials, 2020, 10(36): 2001035.

[38] Zhao R-r, Liang J-x, Huang J-j, et al.. Improving the Ni-rich LiNi_0.5Co_0.2Mn_0.3O₂ cathode properties at high operating voltage by double coating layer of Al₂O₃ and AlPO₄ [J]. Journal of Alloys and Compounds, 2017, 724: 1109-1116.

[39] Kim H, Kim M G, Jeong H Y, et al.. A new coating method for alleviating surface degradation of LiNi_0.6Co_0.2Mn_0.2O₂ cathode material: Nanoscale surface treatment of primary particles [J]. Nano Letters, 2015, 15(3): 2111-2119.

[40] Yoon C S, Ryu H H, Park G T, et al.. Extracting maximum capacity from Ni-rich Li[Ni_0.95Co_0.025Mn_0.025]O₂ cathodes for high-energy-density lithium-ion batteries [J]. Journal of Materials Chemistry A, 2018, 6(9): 4126-4132.

[41] Zhao R-r, Zhang J-l, Lee G H, et al.. The origin of heavy element doping to relieve the lattice thermal vibration of layered materials for high energy density Li ion cathodes [J]. Journal of Materials Chemistry A, 2020, 8(25): 12424-12435.

[42] Liu G-p, Xu N-b, Zou Y, et al.. Stabilizing Ni-rich LiNi_0.83Co_0.12Mn_0.05O₂ with cyclopentyl isocyanate as a novel electrolyte additive [J]. ACS Applied Materials & Interfaces, 2021, 13(10): 12069-12078.

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