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Frontiers of Materials Science

ISSN 2095-025X

ISSN 2095-0268(Online)

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Front. Mater. Sci.    2024, Vol. 18 Issue (3) : 240694    https://doi.org/10.1007/s11706-024-0694-8
A high-capacity and long-lifespan SnO2@K-MnO2 cathode material for aqueous zinc-ion batteries
Xiaoqing Jin1(), Yae Qi1, Yongyao Xia2
1. College of Chemistry and Chemical Engineering, Key Laboratory of Hexi Corridor Resources Utilization of Gansu, Hexi University, Zhangye 734000, China
2. Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Institute of New Energy, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Fudan University, Shanghai 200433, China
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Abstract

Aqueous Zn//MnO2 rechargeable zinc-ion batteries (ZIBs) possess potential applications in electrochemical energy storage due to their safety, low cost, and environmental friendliness. However, manganese dioxide as the cathode material has poor cycle stability and low conductivity. In this work, the SnO2@K-MnO2 (SMO) composite was prepared using the hydrothermal method followed by the treatment with SnCl2 sensitization, and its electrochemical characteristics were examined using SMO as the cathode material for ZIBs. The reversible specific capacity reaches 298.2 mA·h·g−1 at 0.5 A·g−1, and an excellent capacity retention of 86% is realized after 200 cycles, together with a high discharge capacity of 105 mA·h·g−1 at 10 A·g−1 and a long-term cycling life of over 8000 cycles with no apparent capacity fade. This cathode exhibits a long cycle life up to 2000 cycles at 2 A·g−1 with the mass loading of 5 mg·cm−2, and the battery maintains the capacity of 80%. The reversible co-embedding mechanism of H+/Zn2+ in such a Zn//SMO battery was confirmed by XRD and SEM during the charge/discharge process. This work can enlighten and promote the development of advanced cathode materials for ZIBs.

Keywords zinc ion battery      SnO2@K-MnO2      cathode material      energy storage mechanism     
Corresponding Author(s): Xiaoqing Jin   
Issue Date: 08 August 2024
 Cite this article:   
Xiaoqing Jin,Yae Qi,Yongyao Xia. A high-capacity and long-lifespan SnO2@K-MnO2 cathode material for aqueous zinc-ion batteries[J]. Front. Mater. Sci., 2024, 18(3): 240694.
 URL:  
https://academic.hep.com.cn/foms/EN/10.1007/s11706-024-0694-8
https://academic.hep.com.cn/foms/EN/Y2024/V18/I3/240694
Fig.1  (a) Schematic illustration of the synthetic procedure for SnO2@K-MnO2. (b) XRD patterns of SMO samples and SnO2. (c) Raman spectra of SMO-0 and SMO-2. (d) TGA curves of SMO-0 and SMO-2.
Fig.2  (a)(d) SEM images, (b)(e) TEM images, and (c)(f) HRTEM images of SMO-0 (upper panels) and SMO-2 (middle panels). (g) Element mapping images of Mn, Sn, O, and K in SMO-2 (bottom panels).
Fig.3  (a) The full XPS survey spectrum of SMO-2. (b)(c)(d)(e) High-resolution XPS spectra of K 2p, Mn 2p, O 1s, and Sn 3d derived from SMO-2.
Fig.4  Electrochemical performances of Zn//SMO-0, 1, 2, 3 batteries under different conditions: (a) CV curves at 0.2 mV·s?1 for all Zn//SMO batteries; (b) charge/discharge profiles at 0.5 A·g?1 for all Zn//SMO batteries; (c) cycling performances at 0.5 A·g?1 for all Zn//SMO batteries; (d) rate capabilities at 0.1–10 A·g?1 for all Zn//SMO batteries; (e) charge/discharge profiles of the Zn//SMO-2 battery at different current densities from 0.1 to 10 A·g?1; (f) ragone plots for comparison between the Zn//SMO-2 battery and other reported ZIBs comprising manganese-based materials; (g) long cycle performances at 10 A·g?1 for all Zn//SMO batteries; (h) rate performances of the Zn//SMO-2 battery at different current densities from 0.2 to 10 A·g?1 with various mass loadings; (i) cycle performances of the Zn//SMO-2 battery at the current density of 2 A·g?1 with various mass loadings; (j) element content analyses of dissolved Mn2+ in the electrolyte during the cycling processes of SMO-0 and SMO-2.
Fig.5  Electrochemical kinetic analysis on the SMO-2 cathode: (a) CV curves at various scan rates; (b) relationship between the peak current and the scan rate; (c) fitting result of the CV capacitance at 1.0 mV·s?1 reflecting contributions from both the capacitive behavior and the intercalation reaction; (d) diffusion- and capacitance-controlled contributions at different scan rates; (e) a discharge GITT curve at 0.2 A·g?1; (f) relationship between the H+/Zn2+ diffusion coefficient and the specific capacity.
Fig.6  The energy storage mechanism of the SMO-2 cathode: (a) charge/discharge curve; (b) ex situ XRD patterns at various charge/discharge states marked in panel (a); (c)(d)(e)(f)(g)(h) corresponding SEM images collected at States A (panel (c)), B (panel (d)), C (panel (e)), D (panel (f)), E (panel (g)), and F (panel (h)); (i) the insertion/extraction mechanism of H+/Zn2+ in the two-step discharge/charge process for the Zn//SMO-2 battery.
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