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Research Article

Unlocking iron-based mixed-phosphate cathode for sodium-ion batteries through off-stoichiometry

Zhaolu Liu1, Yongjie Cao1,2,§( ), Ning Wang1, Hui Yang1, Hao Zhang1, Xinyue Xu1, Nan Wang2, Jie Xu3, Yao Liu4, Junxi Zhang1,§( ), Yongyao Xia2,§( )
Shanghai Key Laboratory of Materials Protection and Advanced Materials in Electric Power, Shanghai University of Electric Power, Shanghai 200090, China
Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, China
School of Materials Science and Engineering, Anhui University of Technology, Ma’anshan 243002, China
Key Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800, China

§ Yongjie Cao, Junxi Zhang, and Yongyao Xia contributed equally to this work.

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Graphical Abstract

By incorporating different proportions of phosphate NaFePO4 into the off-stoichiometric pyrophosphate Na3.12Fe2.44(P2O7)2 system, we successfully synthesized novel off-stoichiometric mixed-phosphates Na3.12+xFe2.44+x(P2O7)2(PO4)x, and investigated their electrochemical performance.

Abstract

The off-stoichiometric iron-based phosphate (Na3.12Fe2.44(P2O7)2, denoted as Na3.12) as a low cost and high structure stability cathode material has been widely studied for sodium-ion batteries (SIBs). However, the lower theoretical specific capacity (117 mAh·g−1) has seriously limited its practical application. In this work, we incorporate varying proportion of sodium-iron phosphate (NaFePO4) into the Na3.12 to form a series of new high specific capacity mixed-phosphates Na3.12+xFe2.44+x(P2O7)2(PO4)x cathode materials for SIBs. After optimizing the introduction amount of NaFePO4 into Na3.12, the practical reversible of Na3.12+xFe2.44+x(P2O7)2(PO4)x increased from 92 to 125.2 mAh·g−1. The nano-size Na5.12Fe4.44(P2O7)2(PO4)2 cathode material shows a reversible specific capacity of 125.2 mAh·g−1 at 0.1 C in SIBs. Even at 60 C, it still exhibits a reversible specific capacity of 93.3 mAh·g−1 and keeps a capacity retention ratio of 87% after 3000 cycles at 20 C. Thereby, we present a novel approach to design a series of off-stoichiometric mixed-phosphates cathode materials for SIBs.

Keywords

sodium-ion batteriescathode materialiron-based mixed-phosphatesoff-stoichiometric

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Nano Research
Volume 17 Issue 9,
September 2024
Pages 8119-8125
DOI: 10.1007/s12274-024-6804-1
Cite this article:
Liu Z, Cao Y, Wang N, et al. Unlocking iron-based mixed-phosphate cathode for sodium-ion batteries through off-stoichiometry. Nano Research, 2024, 17(9): 8119-8125. https://doi.org/10.1007/s12274-024-6804-1
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Received: 29 April 2024
Revised: 30 May 2024
Accepted: 02 June 2024
Published: 11 July 2024
© Tsinghua University Press 2024
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