Enhancing the Cycling and Rate Performance of NaNi1/3Fe1/3Mn1/3O2 Cathodes by La/Al Codoping

Chengzuo Gong; Gaoxu Han; Jialin Lin; Qiangfeng Zhang; Binbin Wang; Menghao Yang; Zhenghong Huang; Chunxiao Zhang; Weifeng Wei

doi:10.1021/acsami.4c12230

Enhancing the Cycling and Rate Performance of NaNi_1/3Fe_1/3Mn_1/3O₂ Cathodes by La/Al Codoping

ACS Appl Mater Interfaces. 2024 Sep 25;16(38):50961-50971. doi: 10.1021/acsami.4c12230. Epub 2024 Sep 13.

Authors

Chengzuo Gong¹, Gaoxu Han², Jialin Lin¹, Qiangfeng Zhang¹, Binbin Wang¹, Menghao Yang³, Zhenghong Huang⁴, Chunxiao Zhang¹, Weifeng Wei¹

Affiliations

¹ Powder Metallurgy Research Institute, State Key Laboratory of Powder Metallurgy, Central South University, Changsha, Hunan 410083, P. R. China.
² School of Chemical and Environmental Engineering, China University of Mining and Technology (Beijing), Beijing 100083, P. R. China.
³ School of Materials Science and Engineering, Tongji University, Shanghai 201804, P. R. China.
⁴ School of Materials Science and Engineering, Tsinghua University, Beijing 100084, P. R. China.

PMID: 39271243
DOI: 10.1021/acsami.4c12230

Abstract

O3-type layered oxides hold significant promise as the material for cathodes in sodium-ion batteries for their favorable electrochemical properties, while irreversible structural degradation and harmful phase transitions during cyclic operation limit the practical application of these materials. In this work, we proposed a La³⁺/Al³⁺ codoping strategy in O3-Na(Ni_1/3Mn_1/3Fe_1/3)O₂ cathode materials and found that batteries with the Na (Ni_1/3Mn_1/3Fe_1/3)_0.998La_0.001Al_0.001O₂ (NFM-La/Al) cathodes exhibited not only promoted capacity from 135.80 to 170.42 mAh g^-1 at 0.2 C but also significantly enhanced cycling stability, with a 10% improvement in capacity retention compared with NFM cathodes after 300 cycles. Particularly, their rate performance was significantly improved as well. XRD and XPS tests indicated that La could expand the c-axis of NFM due to its larger ionic radius and thus significantly increased Na⁺ ion diffusion efficiency, and in addition, Al doping could effectively increase the content of Ni²⁺ and Mn⁴⁺ and thus greatly alleviated the negative Jahn-Teller effect caused by Mn³⁺. Moreover, consistent with XRD analyses, DFT calculations further substantiated the effectiveness of the La/Al codoping strategy by demonstrating the detailed atom substitution mechanism in the NFM crystal lattice. The boosted structure stability and Na⁺ diffusion kinetics may enhance the potential for practical applications of O3-type oxide cathodes.

Keywords: DFT calculations; O3-Na(Ni1/3Mn1/3Fe1/3) O2; cycling stability; dual-ion doping; sodium-ion battery.