Stabilizing Layered LiCoO₂ Cathode in Aqueous Electrolytes through a Surface-to-Bulk Niobium Modification

Abstract

LiCoO₂ is promising for aqueous lithium-ion batteries due to its simple production processes and high energy density. However, LiCoO₂ exhibits poor cycle life in aqueous electrolytes, primarily attributed to H⁺ intercalation, interfacial reactions, and irreversible phase transformation, which substantially impedes its practical application. Herein, an integrated surface-to-bulk Nb modification strategy combining LiNbO₃ surface coating and gradient Nb doping (N-LCO@LNO) is proposed to enhance the cycling stability of LiCoO₂. The LiNbO₃ surface coating serves as a physical barrier to suppress side reactions, while the gradient Nb doping stabilizes the bulk structure and inhibits spinel phase transition. Density functional theory calculations further reveal that this synergistic modification strategy can significantly suppress the structural degradation induced by electrophilic attack of H⁺. As a result, the N-LCO@LNO electrode delivers a high-rate capability of 117.1 mAh g⁻¹ at 4 C and a long-life stability with 71.4% capacity retention after 100 cycles at 0.5 C, far outperforming the unmodified LiCoO₂ electrode with only 11.1% capacity retention. This study presents a highly promising modification strategy that facilitates the effective utilization of LiCoO₂ in aqueous electrolytes.

Keywords

aqueous electrolyte / coating / cycling stability / doping / lithium cobalt oxide

References

[1] Y. Liang, Y. Yao, Nat. Rev. Mater. 2023, 8, 109.

[2] Y. Wang, T. Ou, Y. Dong, L. Chen, Y. Huang, D. Sun, W. Qiang, X. Pei, Y. Li, Y. Tan, Adv. Mater. 2024, 36, 2311009.

[3] W. Li, J. R. Dahn, D. S. Wainwright, Science 1994, 264, 1115.

[4] Y. Deng, C. Xing, C. Li, Y. Zhou, Z. Peng, L. Fei, C. Zhi, T. Wang, Adv. Funct. Mater. 2025, 35, 2416566.

[5] X. Guo, H. He, S. Zhao, H. Dong, P. R. Shearing, R. Jervis, J. Lin, Energy Storage Mater 2024, 70, 103505.

[6] M. Wu, Z. Zhou, Interdiscip. Mater. 2023, 2, 231.

[7] N. Y. Park, S. B. Kim, M. C. Kim, S. M. Han, D. H. Kim, M. S. Kim, Y. K. Sun, Adv. Energy Mater. 2023, 13, 2301530.

[8] Z. Sun, J. Zhao, M. Zhu, J. Liu, Adv. Energy Mater. 2024, 14, 2303498.

[9] D. Wu, C. Zhu, H. Wang, J. Huang, G. Jiang, Y. Yang, G. Yang, D. Tang, J. Ma, Angew. Chem. Int. Ed. 2024, 63, e202315608.

[10] H. Ma, F. Wang, M. Shen, Y. Tong, H. Wang, H. Hu, Small Methods 2024, 8, 2300820.

[11] S. Posada-Pérez, G. Hautier, G.-M. Rignanese, J. Phys. Chem. C 2022, 126, 110.

[12] H. Oh, H. Yamagishi, T. Ohta, H. R. Byon, Mater. Chem. Front. 2021, 5, 3657.

[13] L. Xue, Q. Zhang, Y. Huang, H. Zhu, L. Xu, S. Guo, X. Zhu, H. Liu, Y. Huang, J. Huang, Adv. Mater. 2022, 34, 2108541.

[14] L. Xue, C. Wang, H. Liu, H. Li, T. Chen, Z. Shi, C. Qiu, M. Sun, Y. Huang, J. Huang, J. Sun, P. Xiong, J. Zhu, H. Xia, Adv. Sci. 2022, 9, 2202194.

[15] X. Gu, J. L. Liu, J. H. Yang, H. J. Xiang, X. G. Gong, Y. Y. Xia, J. Phys. Chem. C 2011, 115, 12672.

[16] H. Oh, S. J. Shin, E. Choi, H. Yamagishi, T. Ohta, N. Yabuuchi, H. G. Jung, H. Kim, H. R. Byon, JACS Au 2023, 3, 1392.

[17] L. Liang, M. Su, Z. Sun, L. Wang, L. Hou, H. Liu, Q. Zhang, C. Yuan, Sci. Adv. 2024, 10, eado4472.

[18] L. Li, L. Fu, M. Li, C. Wang, Z. Zhao, S. Xie, H. Lin, X. Wu, H. Liu, L. Zhang, Q. Zhang, L. Tan, J. Energy Chem. 2022, 71, 588.

[19] M. Li, S. Yang, B. Li, Interdiscip. Mater. 2024, 3, 805.

[20] T. Teranishi, Y. Yoshikawa, M. Yoneda, A. Kishimoto, J. Halpin, S. Brien, M. Modreanu, I. M. Povey, ACS Appl Energy Mater 2018, 1, 3277.

[21] D. P. Singh, Y. A. Birkhölzer, D. M. Cunha, T. Dubbelink, S. Huang, T. A. Hendriks, C. Lievens, M. Huijben, ACS Appl Energy Mater 2021, 4, 5024.

[22] X. Wang, Q. Wu, S. Li, Z. Tong, D. Wang, H. L. Zhuang, X. Wang, Y. Lu, Energy Storage Mater 2021, 37, 67.

[23] J. Wei, Y. Ji, D. Liang, B. Chen, C. Jiang, X. Li, Ceram. Int. 2022, 48, 10288.

[24] Z. Sun, J. Pan, W. Chen, H. Chen, S. Zhou, X. Wu, Y. Wang, K. Kim, J. Li, H. Liu, Y. Yuan, J. Wang, D. Su, D.-L. Peng, Q. Zhang, Adv. Energy Mater. 2024, 14, 2303165.

[25] S. Song, Y. Li, K. Yang, Z. Chen, J. Liu, R. Qi, Z. Li, C. Zuo, W. Zhao, N. Yang, M. Zhang, F. Pan, J Mater Chem A 2021, 9, 5702.

[26] W. Zhang, F. Cheng, M. Wang, J. Xu, Y. Li, S. Sun, Y. Xu, L. Wang, L. Xu, Q. Li, C. Fang, Y. Lu, J. Han, Adv. Funct. Mater. 2023, 33, 2304008.

[27] A. Glass, K. Nassau, T. Negran, J. Appl. Phys. 1978, 49, 4808.

[28] F. Zhang, Y. Liang, Z. Ye, L. Deng, Y. Guo, P. Qiu, P. Jia, Q. Zhang, L. Zhang, Chin. Chem. Lett. 2024, 35, 108655.

[29] B. Wang, B. Xu, T. Liu, P. Liu, C. Guo, S. Wang, Q. Wang, Z. Xiong, D. Wang, X. S. Zhao, Nanoscale 2014, 6, 986.

[30] Y. Yan, Q. Fang, X. Kuai, S. Zhou, J. Chen, H. Zhang, X. Wu, G. Zeng, Z. Wu, B. Zhang, Adv. Mater. 2024, 36, 2308656.

[31] C. Shen, Y. Liu, L. Hu, W. Li, X. Liu, Y. Shi, Y. Jiang, B. Zhao, J. Zhang, Nano Energy 2022, 101, 107555.

[32] P. He, M. Zhang, J. Wu, Y. Li, Y. Wang, Y. Yan, D. Zhang, X. Sun, J. Alloys Compd. 2023, 967, 171822.

[33] J. Ping, S. Rauf, Z. Tayyab, C. Yang, Ceram. Int. 2021, 47, 16460.

[34] N. A. Abdul Aziz, M. De Cunha, T. K. Abdullah, A. A. Mohamad, Int. J. Energy Res. 2017, 41, 289.

[35] X. Wang, Q. Qu, Y. Hou, F. Wang, Y. Wu, Chem. Commun. 2013, 49, 6179.

[36] X. L. Zeng, Y. Y. Huang, F. L. Luo, Y. B. He, D. G. Tong, J. Solgel Sci. Technol. 2010, 54, 139.

[37] P. Man, B. He, Q. Zhang, C. Li, Z. Zhou, Q. Li, W. Xu, G. Hong, Y. Yao, ACS Appl. Mater. Interfaces 2020, 12, 25700.

[38] H. Qin, Z. P. Song, H. Zhan, Y. H. Zhou, J. Power Sources 2014, 249, 367.

[39] R. Ruffo, F. La Mantia, C. Wessells, R. A. Huggins, Y. Cui, Solid State Ionics 2011, 192, 289.

[40] A. Van der Ven, M. Aydinol, G. Ceder, G. Kresse, J. Hafner, Phys. Rev. B 1998, 58, 2975.

[41] K. Maher, R. Yazami, J. Power Sources 2014, 247, 527.

[42] S. Mao, Z. Shen, W. Zhang, Q. Wu, Z. Wang, Y. Lu, Adv. Sci. 2022, 9, 2104841.

[43] H. Y. Asl, A. Manthiram, Science 2020, 369, 140.

[44] G. Kresse, J. Hafner, Phys. Rev. B 1993, 47, 558.

[45] P. E. Blöchl, Phys. Rev. B 1994, 50, 17953.

[46] J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 1996, 77, 3865.

[47] G. Henkelman, H. Jónsson, J. Chem. Phys. 2000, 113, 9978.

[48] C. J. Bartel, S. L. Millican, A. M. Deml, J. R. Rumptz, W. Tumas, A. W. Weimer, S. Lany, V. Stevanović, C. B. Musgrave, A. M. Holder, Nat. Commun. 2018, 9, 4168.

[49] X. Xu, L. Li, J. Huang, H. Jin, X. Fang, W. Liu, N. Zhang, H. Wang, X. Wang, ACS Catal. 2018, 8, 8033.

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