Improved Reversible Capacity and Cycling Stability by Linear (N=O) Anions in Fe[Fe(CN)5 NO] as Sodium-Ion Battery Cathode

Qinghao Han; Ya'nan Hu; Shuting Gao; Zonghua Yang; Xingjun Liu; Cuiping Wang; Jiajia Han

doi:10.1002/cssc.202300823

Improved Reversible Capacity and Cycling Stability by Linear (N=O) Anions in Fe[Fe(CN)₅ NO] as Sodium-Ion Battery Cathode

ChemSusChem. 2023 Oct 20;16(20):e202300823. doi: 10.1002/cssc.202300823. Epub 2023 Aug 25.

Authors

Qinghao Han^{1

2}, Ya'nan Hu^{1

2}, Shuting Gao^{1

2}, Zonghua Yang^{1

2}, Xingjun Liu³, Cuiping Wang^{1

2}, Jiajia Han^{1

2}

Affiliations

¹ College of Materials and Fujian Key Laboratory of Surface and Interface Engineering for High Performance Materials, Xiamen University, Xiamen, 361005, P. R. China.
² Xiamen Key Laboratory of High Performance Metals and Materials, Xiamen University, Xiamen, 361005, P. R. China.
³ School of Materials Science and Engineering, and Institute of Materials Genome & Big Data, Harbin Institute of Technology, Shenzhen, 518055, P. R. China.

PMID: 37552229
DOI: 10.1002/cssc.202300823

Abstract

Prussian blue analogues (PBAs) are promising cathode materials for sodium-ion batteries (SIBs) due to their tunable chemistry, open channel structure, and low cost. However, excessive crystal water and volume expansion can negatively impact the lifetime of actual SIBs. In this study, a novel iron nitroprusside: Fe[Fe(CN)₅ NO] (PBN) was synthesized to effectively eliminate the detrimental effects of crystal water on the reversible capacity and cycling stability of PBA materials. Experiments and DFT calculations demonstrated that PBN has lower crystal water and volume expansion compared to Fe[Fe(CN)₆ ] (PB). Also, the N=O bond in PBN significantly reduces the diffusion potential of Na⁺ in the skeleton. Without any modification, the cathode material exhibited a capacity of up to 148.6 mAh g^-1 at 50 mA g^-1 as well as maintained 102.9 mAh g^-1 after 200 cycles. This work expands our knowledge of the crystal structure of PBA cathode materials and facilitates the rational design of high-quality PBA cathodes for SIBs.

Keywords: DFT; Prussian blue analogues; energy storage; hydrothermal method; sodium-ion batteries.

Abstract

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