Citation: Fanjun Kong, Jing Zhang, Yuting Tang, Chencheng Sun, Chunfu Lin, Tao Zhang, Wangsheng Chu, Li Song, Liang Zhang, Shi Tao. Introducing high-valence element into P2-type layered cathode material for high-rate sodium-ion batteries[J]. Chinese Chemical Letters, ;2025, 36(8): 110993. doi: 10.1016/j.cclet.2025.110993 shu

Introducing high-valence element into P2-type layered cathode material for high-rate sodium-ion batteries

Fanjun Kong ^{a, 1} ,
Jing Zhang ^{a, 1} ,
Yuting Tang ^a ,
Chencheng Sun ^a ,
Chunfu Lin ^{c, *,} ,
Tao Zhang ^e ,
Wangsheng Chu ^d ,
Li Song ^d ,
Liang Zhang ^{b, *,} ,
Shi Tao ^{a, *,}

a.
School of Electronic and Information Engineering, Jiangsu Laboratory of Advanced Functional Materials, Changshu Institute of Technology, Changshu 215500, China
b.
Institute of Functional Nano & Soft Materials (FUNSOM), Soochow University, Suzhou 215123, China
c.
College of Physics, Donghua University, Shanghai 201620, China
d.
National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029, China
e.
School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore

linchunfu@dhu.edu.cn

liangzhang2019@suda.edu.cn

taoshi@cslg.edu.cn

Received Date: 7 November 2024
Revised Date: 18 February 2025
Accepted Date: 20 February 2025
Available Online: 21 February 2025

Figures(4)

P2-type layered transition-metal oxides with high energy density and rich variety have attracted extensive attention for sodium-ion batteries (SIBs) in grid-scale energy storage application, but they usually suffer from sluggish kinetics and large volume change upon cycling. Herein, we designed a high-performance P2-type Na_0.67Ni_0.31Mn_0.67Mo_0.02O₂ (NNMMO) cathode with regulated electronic environment and Na⁺ zigzag ordering modulation via high-valence Mo⁶⁺ stabilization engineering. The achieved NNMMO cathode exhibits a high-rate capability with a reversible capacity of 77.2 mAh/g at 10 C and a long cycle life with a capacity retention of 75% at 2 C after 1000 cycles. In addition, in situ X-ray diffraction and ex-situ X-ray absorption fine structure spectroscopy characterizations verify that the presence of Mo⁶⁺ also stabilizes the desodiated structure through a pinning effect, achieving an extremely low volume change of 1.04% upon Na⁺ extraction. The quantified diffusional analysis and theoretical calculations demonstrate that the Mo⁶⁺-doping improves the Na⁺ diffusion kinetics, optimizes the energy band structure and enhances the TM-O bond strength. Additionally, the as-fabricated pouch cells by paring NNMMO cathode and hard carbon anode show impressive cycling stability with an energy density of 296.7 Wh/kg. This study broadens the perspective for high-valence metal ion doping to obtain superior cathode materials and pave the way for developing high-energy-density SIBs.
- Layered transition-metal oxides,
- Mo doping,
- X-ray absorption fine structure,
- High-rate performance,
- Sodium-ion batteries
1. [1]
  A. Rudola, R. Sayers, C.J. Wright, J. Barker, Nat. Energy 8 (2023) 215–218. doi: 10.1038/s41560-023-01215-w
2. [2]
  N.T. Aristote, K.Y. Zou, A. Di, et al., Chin. Chem. Lett. 33 (2022) 730–742.
3. [3]
  M. Yuan, H. Liu, F. Ran, Mater. Today 63 (2023) 360–379.
4. [4]
  Q. Wang, S.Y. Chu, S.H. Guo, Chin. Chem. Lett. 31 (2020) 2167–2176.
5. [5]
  X.B. Jia, J.Q. Wang, Y.F. Liu, et al., Adv. Mater. 36 (2024) 2307938.
6. [6]
  J.Q. Wang, Y.F. Zhu, Y. Su, et al., Chem. Soc. Rev. 53 (2024) 4230–4301. doi: 10.1039/d3cs00929g
7. [7]
  B. Peng, G.L. Wan, N. Ahmad, et al., Adv. Energy Mater. 13 (2023) 2300334.
8. [8]
  Q.H. Shi, R.J. Qi, X.C. Feng, et al., Nat. Commun. 23 (2022) 3205.
9. [9]
  Z.B. Liu, J. Wu, J. Zeng, et al., Adv. Energy Mater. 13 (2023) 2301471.
10. [10]
  Y.S. Shi, P.F. Jiang, S.C. Wang, et al., Nat. Commun. 13 (2022) 7888.
11. [11]
  B.W. Xiao, X. Liu, X. Chen, et al., Adv. Mater. 33 (2021) 202107141.
12. [12]
  H.B. Yin, Z. Chen, Y. Peng, et al., Angew. Chem. Int. Ed. 61 (2022) e202113242.
13. [13]
  K. Liu, S.S. Tan, J. Moon, et al., Adv. Energy Mater. 10 (2020) 5894–5899.
14. [14]
  X.X. Yang, S.N. Wang, H. Li, et al., ACS Nano 17 (2023) 18616–18628. doi: 10.1021/acsnano.3c07625
15. [15]
  T. Jin, P.F. Wang, Q.C. Wang, et al., Angew. Chem. Int. Ed. 132 (2020) 14619–14624. doi: 10.1002/ange.202003972
16. [16]
  S. Tao, W. Zhou, D.J. Wu, et al., J. Mater. Sci. Technol. 74 (2021) 230–236.
17. [17]
  P.F. Wang, H.R. Yao, X.Y. Liu, et al., Sci. Adv. 4 (2018) eaar6018.
18. [18]
  H. Xin, L. Lin, R.T. Li, et al., J. Am. Chem. Soc. 144 (2022) 4874–4882. doi: 10.1021/jacs.1c12603
19. [19]
  S.Q. Yuan, L. Yu, G.N. Qian, et al., Nano Lett. 23 (2023) 1743–1751. doi: 10.1021/acs.nanolett.2c04465
20. [20]
  H.X. Ren, L.M. Zheng, Y. Li, et al., Nano Energy 103 (2022) 107765.
21. [21]
  D.M. Dai, X.B. Lai, X.J. Wang, et al., Chin. Chem. Lett. 35 (2024) 109405.
22. [22]
  X.P. Dong, X. Wang, Z.X. Lu, Chin. Chem. Lett. 35 (2024) 108605.
23. [23]
  J.N. Liang, Z.Z. Li, J.G. Cheng, et al., Nano Res. 16 (2023) 4987–4995. doi: 10.1007/s12274-022-5221-6
24. [24]
  H. Liu, H.L. Du, W. Zhao, et al., Energy Storage Mater. 40 (2021) 490–498.
25. [25]
  B. Cao, M.J. Du, Z.R. Guo, et al., Carbon Future 1 (2024) 9200017. doi: 10.26599/cf.2024.9200017
26. [26]
  F.J. Kong, Y.X. Ge, S. Tao, et al., Chin. Chem. Lett. 35 (2024) 108552.
27. [27]
  J.Y. Zhang, S.Y. Ma, J.H. Zhang, et al., Nano Energy 128 (2024) 109814.
28. [28]
  Y. Su, B. Johannessen, S.L. Zhang, et al., Adv. Mater. 35 (2023) 2305149.
29. [29]
  J. Liu, W.Y. Huang, R.B. Liu, et al., Adv. Funct. Mater. 6 (2024) 2315437.
30. [30]
  Y. Jiang, S.L. Chou, Y. Xiao, Chin. Chem. Lett. 36 (2025) 110389.
31. [31]
  X. Wang, X.P. Dong, X.C. Feng, et al., Small Methods 7 (2023) 2201201.
32. [32]
  T. Jin, P.F. Wang, Q.C. Wang, et al., Angew. Chem. Int. Ed. 59 (2020) 202003972.
33. [33]
  T.X. Cai, M.Z. Cai, J.X. Mu, et al., Nano-Micro Lett. 16 (2024) 10.
34. [34]
  X.L. Li, T. Wang, Y.F. Yuan, et al., Adv. Mater. 33 (2021) 2008194.
35. [35]
  T. Zhang, M. Ren, Y.H. Huang, et al., Angew. Chem. Int. Ed. 63 (2024) e202316949.
36. [36]
  H.Y. Yang, Q. Zhang, M.H. Chen, Y. Yang, J.B. Zhao, Adv. Funct. Mater. 34 (2023) 3677–3680.
37. [37]
  Y. Zhang, R. Zhang, Y. Huang, Front. Chem. 7 (2019) 355. doi: 10.1504/ijhpcn.2019.099260
38. [38]
  P.F. Zhou, Z.N. Che, J. Liu, et al., Energy Storage Mater. 57 (2023) 618–627.
39. [39]
  C.L. Zhao, Z.P. Yao, Q.D. Wang, et al., J. Am. Chem. Soc. 142 (2020) 5742–5750. doi: 10.1021/jacs.9b13572
40. [40]
  Z.H. Wu, Ni Y. X, S. Tan, et al., J. Am. Chem. Soc. 145 (2023) 9596–9606. doi: 10.1021/jacs.3c00117
1. [1]
  Xiping Dong , Xuan Wang , Zhixiu Lu , Qinhao Shi , Zhengyi Yang , Xuan Yu , Wuliang Feng , Xingli Zou , Yang Liu , Yufeng Zhao . Construction of Cu-Zn Co-doped layered materials for sodium-ion batteries with high cycle stability. Chinese Chemical Letters, 2024, 35(5): 108605-. doi: 10.1016/j.cclet.2023.108605
2. [2]
  Yan-Jiang Li , Shu-Lei Chou , Yao Xiao . Detecting dynamic structural evolution based on in-situ high-energy X-ray diffraction technology for sodium layered oxide cathodes. Chinese Chemical Letters, 2025, 36(2): 110389-. doi: 10.1016/j.cclet.2024.110389
3. [3]
  Guangchang Yang , Shenglong Yang , Jinlian Yu , Yishun Xie , Chunlei Tan , Feiyan Lai , Qianqian Jin , Hongqiang Wang , Xiaohui Zhang . Regulating local chemical environment in O3-type layered sodium oxides by dual-site Mg²⁺/B³⁺ substitution achieves durable and high-rate cathode. Chinese Chemical Letters, 2024, 35(9): 109722-. doi: 10.1016/j.cclet.2024.109722
4. [4]
  Liangju Zhao , Shiyu Qin , Fei Wu , Limin Zhu , Qing Han , Lingling Xie , Xuejing Qiu , Hongliang Wei , Lanhua Yi , Xiaoyu Cao . Polycarbonyl conjugated porous polyimide as anode materials for high performance sodium-ion batteries. Chinese Chemical Letters, 2025, 36(8): 110246-. doi: 10.1016/j.cclet.2024.110246
5. [5]
  Ruofan Yin , Zhaoxin Guo , Rui Liu , Xian-Sen Tao . Ultrafast synthesis of Na₃V₂(PO₄)₃ cathode for high performance sodium-ion batteries. Chinese Chemical Letters, 2025, 36(2): 109643-. doi: 10.1016/j.cclet.2024.109643
6. [6]
  Huixin Chen , Chen Zhao , Hongjun Yue , Guiming Zhong , Xiang Han , Liang Yin , Ding Chen . Unraveling the reaction mechanism of high reversible capacity CuP₂/C anode with native oxidation PO_x component for sodium-ion batteries. Chinese Chemical Letters, 2025, 36(1): 109650-. doi: 10.1016/j.cclet.2024.109650
7. [7]
  Guang Zeng , Yue Zeng , Huamin Hu , Yaqing Bai , Fangjie Nie , Junfei Duan , Zhaoyong Chen , Qi-Long Zhu . Regulating pore structure and pseudo-graphitic phase of hard carbon anode towards enhanced sodium storage performance. Chinese Chemical Letters, 2025, 36(7): 110122-. doi: 10.1016/j.cclet.2024.110122
8. [8]
  Xuan Wang , Peng Sun , Siteng Yuan , Lu Yue , Yufeng Zhao . P2-type low-cost and moisture-stable cathode for sodium-ion batteries. Chinese Chemical Letters, 2025, 36(5): 110015-. doi: 10.1016/j.cclet.2024.110015
9. [9]
  Yanxue Wu , Xijun Xu , Shanshan Shi , Fangkun Li , Shaomin Ji , Jingwei Zhao , Jun Liu , Yanping Huo . Facile construction of Cu_2-xSe@C nanobelts as anode for superior sodium-ion storage. Chinese Chemical Letters, 2025, 36(6): 110062-. doi: 10.1016/j.cclet.2024.110062
10. [10]
  Jiaojiao Liang , Youming Peng , Zhichao Xu , Yufei Wang , Menglong Liu , Xin Liu , Di Huang , Yuehua Wei , Zengxi Wei . Boron/phosphorus co-doped nitrogen-rich carbon nanofiber with flexible anode for robust sodium-ion battery. Chinese Chemical Letters, 2025, 36(1): 110452-. doi: 10.1016/j.cclet.2024.110452
11. [11]
  Shimei Wu , Yining Li , Lantao Chen , Yufei Zhang , Lingxing Zeng , Haosen Fan . Hexapod cobalt phosphosulfide nanorods encapsulating into multiple hetero-atom doped carbon frameworks for advanced sodium/potassium ion battery anodes. Chinese Chemical Letters, 2025, 36(4): 109796-. doi: 10.1016/j.cclet.2024.109796
12. [12]
  Mingxin Song , Lijing Xie , Fangyuan Su , Zonglin Yi , Quangui Guo , Cheng-Meng Chen . New insights into the effect of hard carbons microstructure on the diffusion of sodium ions into closed pores. Chinese Chemical Letters, 2024, 35(6): 109266-. doi: 10.1016/j.cclet.2023.109266
13. [13]
  Jun Dong , Senyuan Tan , Sunbin Yang , Yalong Jiang , Ruxing Wang , Jian Ao , Zilun Chen , Chaohai Zhang , Qinyou An , Xiaoxing Zhang . Spatial confinement of free-standing graphene sponge enables excellent stability of conversion-type Fe₂O₃ anode for sodium storage. Chinese Chemical Letters, 2025, 36(3): 110010-. doi: 10.1016/j.cclet.2024.110010
14. [14]
  Bin Feng , Tao Long , Ruotong Li , Yuan-Li Ding . Rationally constructing metallic Sn-ZnO heterostructure via in-situ Mn doping for high-rate Na-ion batteries. Chinese Chemical Letters, 2025, 36(2): 110273-. doi: 10.1016/j.cclet.2024.110273
15. [15]
  Long Li , Kang Yang , Chenpeng Xi , Mengchao Li , Borong Li , Gui Xu , Yuanbin Xiao , Xiancai Cui , Zhiliang Liu , Lingyun Li , Yan Yu , Chengkai Yang . Highly-chlorinated inert and robust interphase without mineralization of oxide enhancing high-rate Li metal batteries. Chinese Chemical Letters, 2024, 35(6): 108814-. doi: 10.1016/j.cclet.2023.108814
16. [16]
  Shengyu Zhao , Xuan Yu , Yufeng Zhao . A water-stable high-voltage P3-type cathode for sodium-ion batteries. Chinese Chemical Letters, 2024, 35(9): 109933-. doi: 10.1016/j.cclet.2024.109933
17. [17]
  Fan Wu , Shaoyang Wu , Xin Ye , Yurong Ren , Peng Wei . Research progress of high-entropy cathode materials for sodium-ion batteries. Chinese Chemical Letters, 2025, 36(4): 109851-. doi: 10.1016/j.cclet.2024.109851
18. [18]
  Benjian Xin , Rui Wang , Lili Liu , Zhiqiang Niu . Metal-organic framework derived MnO@C/CNTs composite for high-rate lithium-based semi-solid flow batteries. Chinese Journal of Structural Chemistry, 2023, 42(11): 100116-100116. doi: 10.1016/j.cjsc.2023.100116
19. [19]
  Tao Long , Peng Chen , Bin Feng , Caili Yang , Kairong Wang , Yulei Wang , Can Chen , Yaping Wang , Ruotong Li , Meng Wu , Minhuan Lan , Wei Kong Pang , Jian-Fang Wu , Yuan-Li Ding . Reinforced concrete-like Na_3.5V_1.5Mn_0.5(PO₄)₃@graphene hybrids with hierarchical porosity as durable and high-rate sodium-ion battery cathode. Chinese Chemical Letters, 2024, 35(4): 109267-. doi: 10.1016/j.cclet.2023.109267
20. [20]
  Xiuwen Xu , Quan Zhou , Yacong Wang , Yunjie He , Qiang Wang , Yuan Wang , Bing Chen . Expanding the toolbox of metal-free organic halide perovskite for X-ray detection. Chinese Chemical Letters, 2024, 35(9): 109272-. doi: 10.1016/j.cclet.2023.109272

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(21)
HTML views(3)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142