Entropy and crystal-facet modulation of P2-type layered cathodes for long-lasting sodium-based batteries

Fang Fu; Xiang Liu; Xiaoguang Fu; Hongwei Chen; Ling Huang; Jingjing Fan; Jiabo Le; Qiuxiang Wang; Weihua Yang; Yang Ren; Khalil Amine; Shi-Gang Sun; Gui-Liang Xu

doi:10.1038/s41467-022-30113-0

Entropy and crystal-facet modulation of P2-type layered cathodes for long-lasting sodium-based batteries

Nat Commun. 2022 May 20;13(1):2826. doi: 10.1038/s41467-022-30113-0.

Authors

Fang Fu^#¹, Xiang Liu^#², Xiaoguang Fu^#³, Hongwei Chen³, Ling Huang⁴, Jingjing Fan⁴, Jiabo Le⁴, Qiuxiang Wang³, Weihua Yang³, Yang Ren⁵, Khalil Amine^{6

7

8}, Shi-Gang Sun⁹, Gui-Liang Xu¹⁰

Affiliations

¹ College of Materials Science and Engineering, Huaqiao University, Xiamen, 361021, China. fufang@hqu.edu.cn.
² Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL, 60439, United States.
³ College of Materials Science and Engineering, Huaqiao University, Xiamen, 361021, China.
⁴ State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
⁵ X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Lemont, IL, 60439, United States.
⁶ Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL, 60439, United States. amine@anl.gov.
⁷ Materials Science and Engineering, Stanford University, Stanford, CA, United States. amine@anl.gov.
⁸ Materials Science and Nano-engineering, Mohammed VI Polytechnic University, Lot 660 Hay Moulay Rachid, Ben Guerir, Morocco. amine@anl.gov.
⁹ State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China. sgsun@xmu.edu.cn.
¹⁰ Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL, 60439, United States. xug@anl.gov.

^# Contributed equally.

Abstract

P2-type sodium manganese-rich layered oxides are promising cathode candidates for sodium-based batteries because of their appealing cost-effective and capacity features. However, the structural distortion and cationic rearrangement induced by irreversible phase transition and anionic redox reaction at high cell voltage (i.e., >4.0 V) cause sluggish Na-ion kinetics and severe capacity decay. To circumvent these issues, here, we report a strategy to develop P2-type layered cathodes via configurational entropy and ion-diffusion structural tuning. In situ synchrotron X-ray diffraction combined with electrochemical kinetic tests and microstructural characterizations reveal that the entropy-tuned Na_0.62Mn_0.67Ni_0.23Cu_0.05Mg_0.07Ti_0.01O₂ (CuMgTi-571) cathode possesses more {010} active facet, improved structural and thermal stability and faster anionic redox kinetics compared to Na_0.62Mn_0.67Ni_0.37O₂. When tested in combination with a Na metal anode and a non-aqueous NaClO₄-based electrolyte solution in coin cell configuration, the CuMgTi-571-based positive electrode enables an 87% capacity retention after 500 cycles at 120 mA g^-1 and about 75% capacity retention after 2000 cycles at 1.2 A g^-1.

Abstract

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