P2/P3 Biphasic layered oxide cathode enabled by additional electron-holes on oxygen for high-capacity sodium-ion batteries

doi:10.1016/j.jmst.2025.02.072

Abstract

Abstract: Layered transition metal (TM) oxides have gained significant attention for achieving high specific capacity and energy density utilizing the lattice oxygen redox for sodium-ion batteries. However, the highly oxidized lattice oxygen cannot be fully reduced due to irreversible structural deformation, phase transition, and sluggish kinetics. Herein, the Cobalt (Co) content was tuned to synthesize a P2/P3- biphasic layered oxide cathode Na_0.72Li_0.24Co_0.12Mn_0.64O₂ (NLM-Co12%), which exhibits pronounced lattice oxygen activity, leading to exceptional capacity and improved cyclability with superior structural stability. The distinct honeycomb ordering induces highly delocalized π-type interactions that generate additional electron holes on oxygen, providing a record energy density and specific capacity of 767.98 Wh kg^-1 and 287.19 mAh g^-1, respectively. The strategic incorporation of Co in the TM layers mitigates the sluggish kinetics during the electrochemical reactions and improves the diffusion kinetics. The addition of electron holes on Oxygen (O) is comprehensively investigated through different electrochemical and state-of-the-art spectroscopic techniques. Furthermore, in situ-XRD reveals the phase transition during Na⁺ insertion/extraction is eliminated due to the synergistic effect of the P2/P3 biphasic structure achieving superior structural stability. Benefiting from the superstructure ordering and P2/P3 biphasic structure, the NLM-Co12% electrode demonstrates simultaneously high lattice-oxygen activity and excellent structural stability, thus resulting in remarkable energy density and specific capacity.

Key words: P2/P3 Biphasic, Anionic redox, Electron holes, Lattice-oxygen redox, Energy density, Sodium-ion batteries

Hassan Muhammad Mudassir, Chenghao Xie, Fanjie Xia, Rui Fang, Qiushuang Chen, Zhaopei Liu, Tiancheng Dong, Fang Liu, Shan Hu, Jinsong Wu. P2/P3 Biphasic layered oxide cathode enabled by additional electron-holes on oxygen for high-capacity sodium-ion batteries[J]. J. Mater. Sci. Technol., 2025, 238: 230-237.

References

[1] C. Zhao, Q. Wang, Z. Yao, J. Wang, B. Sánchez-Lengeling, F. Ding, X. Qi, Y. Lu, X. Bai, B.J.S.Li Science, 370(2020), 708-711.
[2] Y. Wang, Z. Feng, P. Cui, W. Zhu, Y. Gong, M.A. Girard, G. Lajoie, J. Trottier, Q. Zhang, L. Gu Nat.Commun., 12(2021), 13.
[3] Y. Li, Q. Zhou, S. Weng, F. Ding, X. Qi, J. Lu, Y. Li, X. Zhang, X. Rong, Y. Lu Nat.Energy, 7(2022), 511-519.
[4] J. Jin, Y. Liu, X. Zhao, H. Liu, S. Deng, Q. Shen, Y. Hou, H. Qi, X. Xing, L. Jiao Angew. Chem. Int. Ed., 62 (2023), Article 202219230.
[5] N. Yabuuchi, M. Nakayama, M. Takeuchi, S. Komaba, Y. Hashimoto, T. Mukai, H. Shiiba, K. Sato, Y. Kobayashi, A. Nakao Nat. Commun., 7 (2016), Article 13814.
[6] R.A. House, U. Maitra, M.A.Pérez-Osorio, J.G. Lozano, L. Jin, J.W. Somerville, L.C. Duda, A. Nag, A. Walters, K.J. Zhou Nature, 577(2020), 502-508.
[7] J.J. Marie, M. Jenkins, J. Chen, G.J. Rees, V. Cellorio, J. Choi, S. Agrestini, M. Garcia-Fernandez, K.J. Zhou, R.A. House, P.G. Bruce Adv. Energy Mater., 14 (2024), Article 2401935.
[8] C. Delmas, C. Fouassier, P. Hagenmuller J. Phys. B, 99 (1980), 81-85.
[9] C. Ma, A. Abulikemu, J. Bao, T. Uchiyama, Y.Y. Xia, X.L. Li, Y. Uchimoto, Y.N. Zhou Small, 19 (2023), Article 2302332.
[10] J. Reed, G. Ceder Chem.Rev., 104(2004), 4513-4534.
[11] A. Urban, A. Abdellahi, S. Dacek, N. Artrith, G. Ceder Phys. Rev. Lett., 119 (2017), Article 176402.
[12] J. Zeng, J. Bao, Y. Zhang, X. Li, C. Ma, R.J. Luo, C.Y. Du, X. Xu, Z. Mei, Z. Qian, Y.N.Zhou J. Energy Chem., 89(2023), 79-88.
[13] B.H. Toby, R.B.Von Dreele J. Appl. Crystallogr., 46(2013), 544-549.
[14] Y. Liu, H.Y. Hu, Y.F. Zhu, D. Peng, J.Y. Li, Y.J. Li, Y. Su, R.R. Tang, S.L. Chou, Y. Xiao Chem. Commun., 60 (2024), 6496-6499.
[15] J.Y. Li, H.Y. Hu, H.W. Li, Y.F. Liu, Y. Su, X.B. Jia, L.F. Zhao, Y.M. Fan, Q.F. Gu, H.J.A.N. Zhang ACS Nano, 18(2024), 12945-12956.
[16] D.A. Kitchaev, J. Vinckevičiūtė, A. Van der Ven J. Am. Chem. Soc., 143(2020), 1908-1916.
[17] R.A. House, G.J. Rees, K. McColl, J.J. Marie, M. García-Fernández, A. Nag, K.J. Zhou, S.J. Cassidy, B.J. Morgan, M. Saiful Islam, P.G.Bruce Nat. Energy, 8(2023), 351-360.
[18] Q. Li, Y. Qiao, S. Guo, K. Jiang, Q. Li, J. Wu, H. Zhou Joule, 2 (2018), 1134-1145.
[19] Z. Huang, X. Li, Z. Chen, P. Li, X. Ji, C. Zhi Nat.Rev. Chem., 7(2023), 616-631.
[20] H. Lu, S. Chu, J. Tian, Q. Wang, C. Sheng, C. Cheng, R. Liu, A.M. D’Angelo, W.K. Pang, L. Zhang, H. Zhou, S. Guo Adv. Funct. Mater., 34 (2024), Article 2305470.
[21] X. Rong, E. Hu, Y. Lu, F. Meng, C. Zhao, X. Wang, Q. Zhang, X. Yu, L. Gu, Y.-S. Hu Li H., Huang X., Yang X.-Q., Dlemas C., Chen L. Joule, 3 (2019), 503-517.
[22] S. Roychoudhury, R. Qiao, Z. Zhuo, Q. Li, Y. Lyu, J.H. Kim, J. Liu, E. Lee, B.J. Polzin, J. Guo, S. Yan, Y. Hu, H. Li, D. Prendergast, W. Yang Energy Environ. Mater., 4(2021), 246-254.
[23] K. Wang, J. Qiu, F. Hou, M. Yang, K. Nie, J. Wang, Y. Hou, W. Huang, W. Zhao, P. Zhang Adv. Energy Mater., 13 (2023), Article 2301216.
[24] N. Voronina, M.Y. Shin, H.J. Kim, N. Yaqoob, O. Guillon, S.H. Song, H. Kim, H.D. Lim, H.G. Jung, Y. Kim, H.K. Lee, K.S. Lee, K. Yazawa, K. Gotoh, P. Kaghazchi, S.T. Myung Adv. Energy Mater., 12 (2022), Article 2103939.
[25] Y. Xiao, J. Xiao, H. Zhao, J. Li, G. Zhang, D. Zhang, X. Guo, H. Gao, Y. Wang, J. Chen, G. Wang, H. Liu Small, 20 (2024), Article 2401957.
[26] Y. Yuan, Q. Wei, S. Yang, X. Zhang, M. Jia, J. Yuan, X. Yan Energy Storage Mater., 50 (2022), 760-782.
[27] J. Wang, Y.F. Zhu, Y. Su, J.X. Guo, S. Chen, H.K. Liu, S.X. Dou, S.L. Chou, Y. Xiao Chem.Soc. Rev., 53(2024), 4230-4301.
[28] N. Yabuuchi, M. Kajiyama, J. Iwatate, H. Nishikawa, S. Hitomi, R. Okuyama, R. Usui, Y. Yamada, S. Komaba Nat.Mater., 11(2012), 512-517.
[29] J.W. Somerville, A. Sobkowiak, N. Tapia-Ruiz, J. Billaud, J.G. Lozano, R.A. House, L.C. Gallington, T. Ericsson, L. Häggström, M.R. Roberts, U. Maitra, P.G.Bruce Energy Environ. Sci., 12(2019), 2223-2232