Citation: Lingjun Li, Yanjie Huang, Zhenxuan Liu, Niu Zhao, Huazhao Liang, Minzheng Zhou, Kangyu Zou, Lei Tan, Tianxiang Ning. Revealing the mechanism of Zr coating modification on Ni-rich cathode materials through solid-phase diffusion[J]. Chinese Chemical Letters, ;2026, 37(7): 111079. doi: 10.1016/j.cclet.2025.111079 shu

Revealing the mechanism of Zr coating modification on Ni-rich cathode materials through solid-phase diffusion

School of Materials Science and Engineering, Changsha University of Science and Technology, Changsha 410114, China

ningtianxiang@csust.edu.cn

Received Date: 10 February 2025
Revised Date: 26 February 2025
Accepted Date: 12 March 2025
Available Online: 12 March 2025

Figures(6)

Ni-rich layered oxides are regarded as one of the most reliable cathode materials for lithium-ion batteries. Modifying the crystal structure through doping with foreign elements and constructing surface coating layers are common modification methods for Ni-rich cathode materials. However, the relationship between the diffusion depth and distribution behavior of foreign elements within the cathode material and the composition of the cathode material has rarely been studied in depth. In this work, by exploring the relationship between element concentration and position in a specially prepared two-substances diffusion couple, the diffusion coefficients between Zr⁴⁺ and transition metal elements TMⁿ⁺ (TM = Ni, Co, Mn; n = 3, 4) were obtained. It was found that the magnitude relationship of their diffusion coefficients is: Zr⁴⁺/Mn⁴⁺ > Zr⁴⁺/Mn³⁺ > Zr⁴⁺/Co³⁺ > Zr⁴⁺/Ni³⁺. Moreover, through the Arrhenius equation, it was determined that the Zr⁴⁺/Mn⁴⁺ diffusion couple has the smallest diffusion activation energy of only 0.43 eV, while the Zr⁴⁺/Ni³⁺ diffusion couple has the largest diffusion activation energy, which is 0.63 eV. In addition, this study designed a specific core-shell structure model based on the microscopic morphology of the prepared cathode precursor particles, accurately predicting the distribution differences of Zr⁴⁺ in cathode materials with different compositions during the actual sintering process. This work explains the reason for the formation of a Li₂ZrO₃ secondary phase coating layer on the surface of Ni-rich cathode material particles from the perspective of diffusion kinetics, providing a strong theoretical basis for the future design of high-performance element-modified Ni-rich cathode materials.
- Ni-rich cathode,
- Diffusion coefficients,
- Diffusion activation energy,
- Li₂ZrO₃ coating layer,
- Diffusion kinetics
1. [1]
  Y. Sun, C. Wang, W. Huang, et al., Angew. Chem. 135 (2023) e202300962. doi: 10.1002/ange.202300962
2. [2]
  L. Ni, H. Chen, J. Gao, et al., ACS Nano 17 (2023) 12759–12773. doi: 10.1021/acsnano.3c03770
3. [3]
  Z. Dai, Y. Liu, X. Lu, et al., Adv. Mater. 36 (2024) 2313500. doi: 10.1002/adma.202313500
4. [4]
  H. Xie, H. Peng, D. Jiang, et al., Chem. Eng. J. 470 (2023) 144051. doi: 10.1016/j.cej.2023.144051
5. [5]
  Z. Cui, A. Manthiram, Angew. Chem. Int. Ed. 62 (2023) e202307243. doi: 10.1002/anie.202307243
6. [6]
  Z.Z. Yu, G.Q. Zhao, F.L. Ji, et al., Rare Met. 42 (2023) 4103–4114. doi: 10.1007/s12598-023-02356-3
7. [7]
  K. Zou, S. Xie, M. Jiang, et al., Chem. Eng. J. 483 (2024) 149189. doi: 10.1016/j.cej.2024.149189
8. [8]
  H. Tang, D. Liu, J. Huang, et al., Chin. Chem. Lett. 36 (2025) 109987. doi: 10.1016/j.cclet.2024.109987
9. [9]
  Y. Zhou, H. Zhang, Y. Wang, et al., ACS Nano 17 (2023) 20621–20633. doi: 10.1021/acsnano.3c07655
10. [10]
  L. Li, L. Fu, M. Li, et al., J. Energy Chem. 71 (2022) 588–594. doi: 10.1016/j.jechem.2022.04.037
11. [11]
  Y. Lv, S. Huang, Y. Zhao, et al., Appl. Energy 305 (2022) 117849. doi: 10.1016/j.apenergy.2021.117849
12. [12]
  B. Jin, Z. Cui, A. Manthiram, Angew. Chem. 135 (2023) e202301241. doi: 10.1002/ange.202301241
13. [13]
  N.Y. Park, G.T. Park, S.B. Kim, et al., ACS Energy Lett. 7 (2022) 2362–2369. doi: 10.1021/acsenergylett.2c01272
14. [14]
  L. Tan, X. Huang, T. Yin, et al., Energy Storage Mater. 71 (2024) 103692. doi: 10.1016/j.ensm.2024.103692
15. [15]
  G.T. Park, B. Namkoong, S.B. Kim, et al., Nat. Energy 7 (2022) 946–954. doi: 10.1038/s41560-022-01106-6
16. [16]
  J. Li, W. Zhong, Q. Deng, et al., Adv. Funct. Mater. 33 (2023) 2300127. doi: 10.1002/adfm.202300127
17. [17]
  Q. Shi, R. Qi, X. Feng, et al., Nat. Commun. 13 (2022) 3205. doi: 10.1038/s41467-022-30942-z
18. [18]
  C. Geng, D. Rathore, D. Heino, et al., Adv. Energy Mater. 12 (2022) 2103067. doi: 10.1002/aenm.202103067
19. [19]
  M. Jiang, P. Wang, Q. Chen, et al., Chin. Chem. Lett. 36 (2025) 110040. doi: 10.1016/j.cclet.2024.110040
20. [20]
  Y.H. Du, H. Sheng, X.H. Meng, et al., Nano Energy 94 (2022) 106901. doi: 10.1016/j.nanoen.2021.106901
21. [21]
  W. Li, S. Zhang, W. Zheng, et al., Adv. Funct. Mater. 33 (2023) 2300791. doi: 10.1002/adfm.202300791
22. [22]
  K. Yang, Y. Yi, G. Hu, et al., Chem. Eng. J. 1 (2024) 152872.
23. [23]
  H. Yang, H.H. Wu, M. Ge, et al., Adv. Funct. Mater. 29 (2019) 1808825. doi: 10.1002/adfm.201808825
24. [24]
  H. Shi, J. Zheng, T. Wan, et al., J. Energy Chem. 101 (2025) 392–401. doi: 10.1016/j.jechem.2024.09.056
25. [25]
  K. Park, D.J. Ham, S.Y. Park, et al., RSC Adv. 10 (2020) 26756–26764. doi: 10.1039/d0ra01543a
26. [26]
  Z. Zhang, B. Hong, M. Yi, et al., Chem. Eng. J. 445 (2022) 136825. doi: 10.1016/j.cej.2022.136825
27. [27]
  Y. Shen, D. Yin, H. Xue, et al., J. Colloid Interface Sci. 663 (2024) 961–970. doi: 10.1016/j.jcis.2024.02.213
28. [28]
  C. Liu, Q. Luo, L. Li, et al., Chem. Eng. J. 500 (2024) 156866. doi: 10.1016/j.cej.2024.156866
29. [29]
  X. Tan, W. Peng, M. Wang, et al., Al., Prog. Nat. Sci. Mater. 33 (2023) 108–115. doi: 10.1016/j.pnsc.2022.12.004
30. [30]
  Z. Wen, Y. Song, H. Shi, et al., J. Energy Storage 98 (2024) 113037. doi: 10.1016/j.est.2024.113037
31. [31]
  J.Q. Peng, Y.Y. Wei, D.M. Liu, et al., Rare Met. 43 (2024) 658–670. doi: 10.1007/s12598-023-02470-2
32. [32]
  K. Zou, M. Jiang, T. Ning, et al., Chem. Eng. J. 97 (2024) 321–331.
33. [33]
  J. Li, R. Doig, J. Camardese, et al., Chem. Mater. 27 (2015) 7765–7773. doi: 10.1021/acs.chemmater.5b03499
34. [34]
  H. Zhao, W.Y.A. Lam, L. Sheng, et al., Adv. Energy Mater. 12 (2022) 2103894. doi: 10.1002/aenm.202103894
35. [35]
  Y. Zhao, J. Li, J.R. Dahn, Chem. Mater. 29 (2017) 5239–5248. doi: 10.1021/acs.chemmater.7b01219
36. [36]
  C. Li, Z. Song, C. Chen, et al., Nat. Energy 5 (2020) 768–776. doi: 10.1038/s41560-020-00692-7
37. [37]
  M. Ghasemi, B. Guo, K. Darabi, et al., Nat. Mater. 22 (2023) 329–337. doi: 10.1038/s41563-023-01488-2
38. [38]
  Q. Fan, J. Yao, S. Zhao, et al., Small 21 (2025) 2409215. doi: 10.1002/smll.202409215
39. [39]
  L. Li, Q. Chen, M. Jiang, et al., Energy Storage Mater. 75 (2025) 104016. doi: 10.1016/j.ensm.2025.104016
40. [40]
  Y.J. Guo, P.F. Wang, Y.B. Niu, et al., Nat. Commun. 12 (2021) 5267. doi: 10.1038/s41467-021-25610-7
41. [41]
  G. Ko, S. Jeong, S. Park, et al., Energy Storage Mater. 60 (2023) 102840. doi: 10.1016/j.ensm.2023.102840
42. [42]
  R. Wang, Y. Sun, K. Yang, et al., J. Energy Chem. 50 (2020) 271–279. doi: 10.1016/j.jechem.2020.03.042
43. [43]
  J. Guo, Y. Li, J. Meng, et al., J. Energy Chem. 74 (2022) 34–44. doi: 10.3390/bioengineering10010034
44. [44]
  J. Ahn, Y. Ha, R. Satish, et al., Adv. Energy Mater. 12 (2022) 2200426. doi: 10.1002/aenm.202200426
45. [45]
  H. Zhu, Z. Wang, L. Chen, et al., Adv. Mater. 35 (2023) 2209357. doi: 10.1002/adma.202209357
46. [46]
  L. Ni, H. Chen, S. Guo, et al., Adv. Funct. Mater. 33 (2023) 2307126. doi: 10.1002/adfm.202307126
47. [47]
  X.M. Fan, Z. Zhang, G.Q. Mao, et al., Rare Met. 42 (2023) 2993–3003. doi: 10.1007/s12598-023-02288-y
48. [48]
  Y. Chu, S. You, Y. Mu, et al., ACS Nano 18 (2024) 23380–23391. doi: 10.1021/acsnano.4c06663
1. [1]
  Mingzhu Jiang , Panqing Wang , Qiheng Chen , Yue Zhang , Qi Wu , Lei Tan , Tianxiang Ning , Lingjun Li , Kangyu Zou . Enabling the Nb/Ti co-doping strategy for improving structure stability and rate capability of Ni-rich cathode. Chinese Chemical Letters, 2025, 36(6): 110040-. doi: 10.1016/j.cclet.2024.110040
2. [2]
  Lingyao Zhang , Chunhui Zhang , Yingjia Sun , Qinglin Yang , Ziwei Guo , Xiaoqi Wang , Kang Wang , Lin Zhang , Kesong Liu , Shichao Niu , Cunming Yu , Lei Jiang . Bioinspired underwater gas diffusion enhanced by superaerophilic stripe. Chinese Chemical Letters, 2026, 37(5): 111720-. doi: 10.1016/j.cclet.2025.111720
3. [3]
  Lumin Zheng , Ying Bai , Chuan Wu . Multi-electron reaction and fast Al ion diffusion of δ-MnO₂ cathode materials in rechargeable aluminum batteries via first-principle calculations. Chinese Chemical Letters, 2024, 35(4): 108589-. doi: 10.1016/j.cclet.2023.108589
4. [4]
  Chen Chen , Jinzhou Zheng , Chaoqin Chu , Qinkun Xiao , Chaozheng He , Xi Fu . An effective method for generating crystal structures based on the variational autoencoder and the diffusion model. Chinese Chemical Letters, 2025, 36(4): 109739-. doi: 10.1016/j.cclet.2024.109739
5. [5]
  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
6. [6]
  Yihan Zhou , Duo Gao , Yaying Wang , Li Liang , Qingyu Zhang , Wenwen Han , Jie Wang , Chunliu Zhu , Xinxin Zhang , Yong Gan . Worm-like micelles facilitate the intestinal mucus diffusion and drug accumulation for enhancing colorectal cancer therapy. Chinese Chemical Letters, 2024, 35(6): 108967-. doi: 10.1016/j.cclet.2023.108967
7. [7]
  Yujie Xie , Kexin Yuan , Beiyang Luo , Haoran Feng , Xian Bao , Jun Ma . Osmotic membranes for municipal wastewater reclamation: Insights into applications, transmembrane diffusion mechanisms and prospects. Chinese Chemical Letters, 2025, 36(7): 110443-. doi: 10.1016/j.cclet.2024.110443
8. [8]
  Yao Wang , Jun Ouyang , Huadong Yuan , Jianmin Luo , Shihui Zou , Jianwei Nai , Xinyong Tao , Yujing Liu . Impact of local amorphous environment on the diffusion of sodium ions at the solid electrolyte interface in sodium-ion batteries. Chinese Chemical Letters, 2025, 36(10): 110412-. doi: 10.1016/j.cclet.2024.110412
9. [9]
  Siyi Zou , Ali Hammad , Jiahao Huang , Yuzhuo Jiang , Bin Tian , Fandi Ning , Wei Li , Qinglin Wen , Xingyu Zhu , Xiaochun Zhou . Gel/nonwoven composite membrane with dual water transport pathways for controlling hydrogen production by regulating water vapor absorption and diffusion. Chinese Chemical Letters, 2026, 37(4): 111619-. doi: 10.1016/j.cclet.2025.111619
10. [10]
  Jiangli Sun , Chaohui Zhang , Yican Zhang , Chunhong Fu , Ruiheng Liang , Zhongzheng Hu , Ge Song , Minghua Zhou . Ag₃PO₄/g-C₃N₄ S-scheme heterojunction photoanode coupled with natural air diffusion electrode for efficient organic pollutants degradation and H₂O₂ generation. Chinese Chemical Letters, 2026, 37(5): 111839-. doi: 10.1016/j.cclet.2025.111839
11. [11]
  Xiaohan Zhang , Bo Xiao . Facilitating ultra-fast lithium ion diffusion in face-centered cubic oxides via over-stoichiometric face-sharing configurations. Chinese Journal of Structural Chemistry, 2025, 44(2): 100419-100419. doi: 10.1016/j.cjsc.2024.100419
12. [12]
  Yu Su , Jinbo Hu , Laiqiang Xu , Xinwen Jiang , Gonggang Liu , Yuanjuan Bai , Yuanyuan Liao , Shanshan Chang , Xiaowei Cheng . Tannin-derived sulfur-doped carbon with tunable porosity and dilated interlayer spacing for reversible Na-ion diffusion. Chinese Chemical Letters, 2026, 37(2): 111210-. doi: 10.1016/j.cclet.2025.111210
13. [13]
  Ruiheng Liang , Huizhong Wu , Zhongzheng Hu , Ge Song , Xuyang Zhang , Omotayo A. Arotiba , Minghua Zhou . Hierarchical Fe-Bi/Bi₇O₉I₃/OVs microspheres coupled with natural air diffusion electrode to achieve efficient heterogeneous visible-light-driven photoelectro-Fenton degradation of tetracycline without aeration. Chinese Chemical Letters, 2025, 36(4): 110136-. doi: 10.1016/j.cclet.2024.110136
14. [14]
  Yajuan Zhang , Jinliang Li , Xi Zhang , Yue Li , Peng Sun , Hao Xu , Likun Pan . Mitigate pressure dependence in sulfide-based all-solid-state batteries via structural and interfacial engineering of Ni-rich cathodes. Acta Physico-Chimica Sinica, 2026, 42(4): 100204-0. doi: 10.1016/j.actphy.2025.100204
15. [15]
  Ruonan Yang , Jiajia Li , Dongmei Zhang , Xiuqi Zhang , Xia Li , Han Yu , Zhanhu Guo , Chuanxin Hou , Gang Lian , Feng Dang . Grain-refining Co_0.85Se@CNT cathode catalyst with promoted Li₂O₂ growth kinetics for lithium-oxygen batteries. Chinese Chemical Letters, 2024, 35(12): 109595-. doi: 10.1016/j.cclet.2024.109595
16. [16]
  Shanyan Huang , Bi Luo , Zixun Zhang , Qi Wang , Guihui Yu , Xudong Bu , Zheng Huang , Xiaowei Wang , Wei-Li Song , Jiafeng Zhang , Shuqiang Jiao . Effect of crystal morphology of nickel-rich cathode materials on electrochemical stability and ion transport kinetics of sulfide-based all-solid-state batteries. Chinese Chemical Letters, 2026, 37(3): 110729-. doi: 10.1016/j.cclet.2024.110729
17. [17]
  Yongjian Li , Xinyu Zhu , Chenxi Wei , Youyou Fang , Xinyu Wang , Yizhi Zhai , Wenlong Kang , Lai Chen , Duanyun Cao , Meng Wang , Yun Lu , Qing Huang , Yuefeng Su , Hong Yuan , Ning Li , Feng Wu . Unraveling the chemical and structural evolution of novel Li-rich layered/rocksalt intergrown cathode for Li-ion batteries. Chinese Chemical Letters, 2024, 35(12): 109536-. doi: 10.1016/j.cclet.2024.109536
18. [18]
  Maomao Liu , Guizeng Liang , Ningce Zhang , Tao Li , Lipeng Diao , Ping Lu , Xiaoliang Zhao , Daohao Li , Dongjiang Yang . Electron-rich Ni2+ in Ni3S2 boosting electrocatalytic CO2 reduction to formate and syngas. Chinese Journal of Structural Chemistry, 2024, 43(8): 100359-100359. doi: 10.1016/j.cjsc.2024.100359
19. [19]
  Yi Zhang , Biao Wang , Chao Hu , Muhammad Humayun , Yaping Huang , Yulin Cao , Mosaad Negem , Yigang Ding , Chundong Wang . Fe–Ni–F electrocatalyst for enhancing reaction kinetics of water oxidation. Chinese Journal of Structural Chemistry, 2024, 43(2): 100243-100243. doi: 10.1016/j.cjsc.2024.100243
20. [20]
  Mingjiao Lu , Zhixing Wang , Gui Luo , Huajun Guo , Xinhai Li , Guochun Yan , Qihou Li , Xianglin Li , Ding Wang , Jiexi Wang . Boosting the performance of LiNi_0.90Co_0.06Mn_0.04O₂ electrode by uniform Li₃PO₄ coating via atomic layer deposition. Chinese Chemical Letters, 2024, 35(5): 108638-. doi: 10.1016/j.cclet.2023.108638

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(13)
HTML views(0)

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