Enabling nickel ferrocyanide nanoparticles for high-performance ammonium ion storage

doi:10.1007/s11705-022-2198-3

Front. Chem. Sci. Eng.

2023, Vol. 17

Issue (2) : 226-235 https://doi.org/10.1007/s11705-022-2198-3

RESEARCH ARTICLE

Enabling nickel ferrocyanide nanoparticles for high-performance ammonium ion storage

Haoxiang Yu^1,², Leiyu Fan², Chenchen Deng², Huihui Yan², Lei Yan², Jie Shu²(

), Zhen-Bo Wang¹(

)

¹. MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, State Key Lab of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150001, China
². School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, China

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Abstract

Prussian blue and its analogs are extensively investigated as a cathode for ammonium-ion batteries. However, they often suffer from poor electronic conductivity. Here, we report a Ni₂Fe(CN)₆/multiwalled carbon nanotube composite electrode material, which is prepared using a simple coprecipitation approach. The obtained material consists of nanoparticles with sizes 30–50 nm and the multiwalled carbon nanotube embedded in it. The existence of multiwalled carbon nanotube ensures that the Ni₂Fe(CN)₆/multiwalled carbon nanotube composite shows excellent electrochemical performance, achieving a discharge capacity of 55.1 mAh·g^–1 at 1 C and 43.2 mAh·g^–1 even at 15 C. An increase in the ammonium-ion diffusion coefficient and ionic/electron conductivity based on kinetic investigations accounts for their high performance. Furthermore, detailed ex situ characterizations demonstrate that Ni₂Fe(CN)₆/multiwalled carbon nanotube composite offers three advantages: negligible lattice expansion during cycling, stable structure, and the reversible redox couple. Therefore, the Ni₂Fe(CN)₆/multiwalled carbon nanotube composite presents a long cycling life and high rate capacity. Finally, our study reports a desirable material for ammonium-ion batteries and provides a practical approach for improving the electrochemical performance of Prussian blue and its analogs.

Keywords nickel ferrocyanides NH₄⁺ electrochemistry Prussian blue aqueous ammonium ion batteries

Corresponding Author(s): Jie Shu,Zhen-Bo Wang

About author:

Changjian Wang and Zhiying Yang contributed equally to this work.

Online First Date: 14 October 2022 Issue Date: 27 February 2023

Cite this article:

Haoxiang Yu,Leiyu Fan,Chenchen Deng, et al. Enabling nickel ferrocyanide nanoparticles for high-performance ammonium ion storage[J]. Front. Chem. Sci. Eng., 2023, 17(2): 226-235.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-022-2198-3
https://academic.hep.com.cn/fcse/EN/Y2023/V17/I2/226

Fig.1 Schematic illustration of the synthesis process of Ni₂Fe(CN)₆/MWCNT.

Fig.2 (a) XRD patterns of Ni₂Fe(CN)₆/MWCNT, Ni₂Fe(CN)₆, and MWCNT; (b) Raman spectra of Ni₂Fe(CN)₆/MWCNT and Ni₂Fe(CN)₆; (c) crystal structure of Ni₂Fe(CN)₆; (d) photograph of Ni₂Fe(CN)₆/MWCNT and Ni₂Fe(CN)₆; (e) thermal gravity analysis curves of Ni₂Fe(CN)₆/MWCNT and Ni₂Fe(CN)₆ under air atmosphere.

Fig.3 SEM of (a, b) Ni₂Fe(CN)₆/MWCNT and (c) Ni₂Fe(CN)₆; (d, e) TEM of Ni₂Fe(CN)₆/MWCNT; (f) HRTEM of Ni₂Fe(CN)₆/MWCNT.

Fig.4 Discharge–charge profiles of (a) Ni₂Fe(CN)₆/MWCNT and (b) Ni₂Fe(CN)₆ at 1 and 15 C (1 C = 60 mAh·g^–1). (c) Cycling performance of Ni₂Fe(CN)₆/MWCNT and Ni₂Fe(CN)₆ at 1 C for the first 5 cycles and at 15 C afterwards. Discharge–charge profiles of (d) Ni₂Fe(CN)₆/MWCNT and (e) Ni₂Fe(CN)₆ at different current rates. (f) Rate performance of Ni₂Fe(CN)₆/MWCNT and Ni₂Fe(CN)₆ at 1, 3, 5, 9, and 15 C.

Fig.5 CV curves of (a) Ni₂Fe(CN)₆/MWCNT and (b) Ni₂Fe(CN)₆ measured at different scan rates from 0.2 to 1.6 mV·s^–1. (c) The linear relationship between the peak current (I_p) and the square root of scan rate (ν^1/2). (d) The diffusion coefficients of ammonium ion for Ni₂Fe(CN)₆/MWCNT and Ni₂Fe(CN)₆ calculated from CV.

Fig.6 (a) Ex situ XRD patterns of Ni₂Fe(CN)₆/MWCNT upon charging/discharging. (b) Lattice parameter a and (c) volume calculated from ex situ XRD patterns. (d) FTIR spectra of Ni₂Fe(CN)₆/MWCNT upon charging/discharging.

Fig.7 XPS spectra of the Fe 2p and Ni 2p peaks for Ni₂Fe(CN)₆/MWCNT electrode at different charge state.

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