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Nano Research 2023, 16(5): 6890-6902 https://doi.org/10.1007/s12274-023-5435-2
Research Article | Issue | Published: 28 February 2023

Moisture stable and ultrahigh-rate Ni/Mn-based sodium-ion battery cathodes via K+ decoration

Show Author's Information Tao Yuan1,§,  Yuanyuan Sun1,§,  Siqing Li1,  Haiying Che2,  Qinfeng Zheng3,  Yongjian Ni4,  Yixiao Zhang3,  Jie Zou4,  Xiaoxian Zang3,5,  Shi-Hao Wei4,  Yuepeng Pang1,  Shuixin Xia1,  Shiyou Zheng1( ),  Liwei Chen3( ),  Zi-Feng Ma2,3( )
School of Materials and Chemistry, University of Shanghai for Science and Technology, Shanghai 200093, China
Zhejiang Natrium Energy Co., Ltd., Shaoxing 312000, China
In-situ Center for Physical Sciences, Shanghai Electrochemical Energy Device Research Center, and Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
Faculty of Electrical Engineering and Computer Science, Ningbo University, Ningbo 315000, China
Key Laboratory of Solar Energy Utilization & Energy Saving Technology of Zhejiang Province, Zhejiang Energy R&D Institute Co., Ltd., Hangzhou 311121, China

§ Tao Yuan and Yuanyuan Sun contributed equally to this work.

Keywords:
cathode, sodium-ion battery, layered oxide material, K+ decoration
Topics:
Energy storageIon batteries
Cite this article:
Yuan T, Sun Y, Li S, et al. Moisture stable and ultrahigh-rate Ni/Mn-based sodium-ion battery cathodes via K+ decoration. Nano Research, 2023, 16(5): 6890-6902. https://doi.org/10.1007/s12274-023-5435-2
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Abstract Full text Electronic supplementary material About this article

As one of the most promising cathodes for sodium-ion batteries (SIBs), the layered transition metal oxides have attracted great attentions due to their high specific capacities and facile synthesis. However, their applications are still hindered by the problems of poor moisture stability and sluggish Na+ diffusion caused by intrinsic structural Jahn–Teller distortion. Herein, we demonstrate a new approach to settle the above issues through introducing K+ into the structures of Ni/Mn-based materials. The physicochemical characterizations reveal that K+ induces atomic surface reorganization to form the birnessite-type K2Mn4O8. Combining with the phosphate, the mixed coating layer protects the cathodes from moisture and hinders metal dissolution into the electrolyte effectively. Simultaneously, K+ substitution at Na site in the bulk structure can not only widen the lattice-spacing for favoring Na+ diffusion, but also work as the rivet to restrain the grain crack upon cycling. The as achieved K+-decorated P2-Na0.67Mn0.75Ni0.25O2 (NKMNO@KM/KP) cathodes are tested in both coin cell and pouch cell configurations using Na metal or hard carbon (HC) as anodes. Impressively, the NKMNO@KM/KP||Na half-cell demonstrates a high rate performance of 50 C and outstanding cycling performance of 90.1% capacity retention after 100 cycles at 5 C. Furthermore, the NKMNO@KM/KP||HC full-cell performed a promising energy density of 213.9 Wh·kg−1. This performance significantly outperforms most reported state-of-the-art values. Additionally, by adopting this strategy on O3-NaMn0.5Ni0.5O2, we further proved the universality of this method on layered cathodes for SIBs.


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Electronic supplementary material
About this article

Moisture stable and ultrahigh-rate Ni/Mn-based sodium-ion battery cathodes via K+ decoration

Show Author's information Tao Yuan1,§, Yuanyuan Sun1,§, Siqing Li1, Haiying Che2, Qinfeng Zheng3, Yongjian Ni4, Yixiao Zhang3, Jie Zou4, Xiaoxian Zang3,5, Shi-Hao Wei4, Yuepeng Pang1, Shuixin Xia1, Shiyou Zheng1( ), Liwei Chen3( ), Zi-Feng Ma2,3( )
School of Materials and Chemistry, University of Shanghai for Science and Technology, Shanghai 200093, China
Zhejiang Natrium Energy Co., Ltd., Shaoxing 312000, China
In-situ Center for Physical Sciences, Shanghai Electrochemical Energy Device Research Center, and Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
Faculty of Electrical Engineering and Computer Science, Ningbo University, Ningbo 315000, China
Key Laboratory of Solar Energy Utilization & Energy Saving Technology of Zhejiang Province, Zhejiang Energy R&D Institute Co., Ltd., Hangzhou 311121, China

§ Tao Yuan and Yuanyuan Sun contributed equally to this work.

Abstract

As one of the most promising cathodes for sodium-ion batteries (SIBs), the layered transition metal oxides have attracted great attentions due to their high specific capacities and facile synthesis. However, their applications are still hindered by the problems of poor moisture stability and sluggish Na+ diffusion caused by intrinsic structural Jahn–Teller distortion. Herein, we demonstrate a new approach to settle the above issues through introducing K+ into the structures of Ni/Mn-based materials. The physicochemical characterizations reveal that K+ induces atomic surface reorganization to form the birnessite-type K2Mn4O8. Combining with the phosphate, the mixed coating layer protects the cathodes from moisture and hinders metal dissolution into the electrolyte effectively. Simultaneously, K+ substitution at Na site in the bulk structure can not only widen the lattice-spacing for favoring Na+ diffusion, but also work as the rivet to restrain the grain crack upon cycling. The as achieved K+-decorated P2-Na0.67Mn0.75Ni0.25O2 (NKMNO@KM/KP) cathodes are tested in both coin cell and pouch cell configurations using Na metal or hard carbon (HC) as anodes. Impressively, the NKMNO@KM/KP||Na half-cell demonstrates a high rate performance of 50 C and outstanding cycling performance of 90.1% capacity retention after 100 cycles at 5 C. Furthermore, the NKMNO@KM/KP||HC full-cell performed a promising energy density of 213.9 Wh·kg−1. This performance significantly outperforms most reported state-of-the-art values. Additionally, by adopting this strategy on O3-NaMn0.5Ni0.5O2, we further proved the universality of this method on layered cathodes for SIBs.

Keywords: cathode, sodium-ion battery, layered oxide material, K+ decoration

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Publication history
Copyright
Acknowledgements

Publication history

Received: 10 October 2022
Revised: 09 December 2022
Accepted: 21 December 2022
Published: 28 February 2023
Issue date: May 2023

Copyright

© Tsinghua University Press 2023

Acknowledgements

Acknowledgements

We acknowledge the support of the National Natural Science Foundation of China (Nos. 52271222, 51971146, 51971147, 52171218, 22005190, and 21938005). We also acknowledge the supports of Shanghai Outstanding Academic Leaders Plan, the Innovation Program of Shanghai Municipal Education Commission (No. 2019-01-07-00-07-E00015), Shanghai Pujiang Program (No. 21PJ1411100), Shanghai Rising-Star Program (Nos. 20QA1407100 and 21QA1406500), the Shanghai Science and Technology Commission (Nos. 21010503100, 20ZR1438400 and 22ZR1443900), Zhejiang Provincial Natural Science Foundation of China (No. LGG22F010017), and the Key R&D Program of Zhejiang Province (Nos. 2019C01155 and 2020C01128).

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