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A non-flammable hydrous organic electrolyte for sustainable zinc batteries

Nature Sustainability volume 5, pages 205–213 (2022)Cite this article

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Abstract

Aqueous zinc (Zn) batteries have long been considered a potentially more sustainable alternative to lithium-ion batteries because of their better environmental compatibility, enhanced safety and cost advantage. However, in the presence of an aqueous electrolyte, the Zn anode is poised to undergo dendrite failure, corrosion and hydrogen evolution, all of which resonate with each other leading to fast performance degradation. Here, in a break from the current aqueous battery path, we report a low-cost hydrous organic electrolyte involving a hydrated Zn(BF4)2 salt and an ethylene glycol solvent, which not only promotes the in situ formation of a favourable ZnF2 passivation layer to protect Zn from dendrite growth and side reactions but also embraces excellent non-flammability. Remarkably, the present Zn anode sustains a long-term cycling over 4,000 h at a current density of 0.5 mA cm−2 with a high Coulombic efficiency of 99.4% and shows an areal capacity as high as 5 mAh cm−2. Equally intriguingly, the electrolyte can run across a wide temperature range from −30 °C to 40 °C without seriously compromising performance. The Zn//V2O5 full cells with our electrolyte also perform much better in terms of capacity retention than a device with an aqueous ZnSO4 electrolyte. Our findings suggest a promising direction for developing electrolyte solutions for practical Zn batteries which combine safety, performance and sustainability.

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Fig. 1: Properties of Zn(BF4)2/EG electrolytes.
Fig. 2: Morphology and composition of the generated ZnF2 layer.
Fig. 3: Electrochemical performance of Zn anodes in the 4 m Zn(BF4)2/EG electrolyte.
Fig. 4: Performance of Zn anodes in different electrolytes over a wide temperature range.
Fig. 5: Performance of Zn//V2O5 full cells in different electrolytes.

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The data that support the findings detailed in this study are available in the article and its Supplementary Information or from the corresponding authors on reasonable request. Source data are provided with this paper.

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Acknowledgements

This research was supported by grants from the National Natural Science Foundation of China (51972223, 51932005 and 51972312), China Postdoctoral Science Foundation (2021M692385), Natural Science Foundation of Tianjin (20JCYBJC01550) and the Local Innovative Research Teams Project of Guangdong Pearl River Talents Programme (2017BT01N111). We thank the National Supercomputer Center in Tianjin for computation support from TianHe-1(A) and the National Supercomputer Center in Guangzhou for computation support from Tianhe-2.

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Author notes

  1. These authors contributed equally: Daliang Han, Changjun Cui.

Authors and Affiliations

  1. Nanoyang Group, State Key Laboratory of Chemical Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin, China

    Daliang Han, Changjun Cui, Zhenxing Wang, Jiachen Gao, Yong Guo, Zhicheng Zhang, Shichao Wu, Zhe Weng & Quan-Hong Yang

  2. Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen, China

    Daliang Han & Feiyu Kang

  3. Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang, China

    Kangyu Zhang & Lichang Yin

  4. Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Fuzhou, China

    Quan-Hong Yang

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Contributions

Q.-H.Y., F.K. and Z.Weng proposed the project; Z.Weng and D.H. conceived the idea; and Z.Weng, F.K. and Q.-H.Y. supervised the project. D.H. and C.C. synthesized the samples and performed the characterizations and electrochemical measurements. K.Z. and L.Y. performed the simulation and data analysis. Z.Wang, Y.G., J.G. and Z.Z. contributed to the structural characterizations and electrochemical measurements. S.W. contributed to the structural and performance analysis. D.H., C.C., Z.Weng and Q.-H.Y. organized and wrote the manuscript. All authors contributed to the discussion and revision of the manuscript at all stages. D.H. and C.C. contributed equally to this work.

Corresponding authors

Correspondence to Zhe Weng, Feiyu Kang or Quan-Hong Yang.

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Additional information

Peer review information Nature Sustainability thanks Antonio Jesús Fernández Romero and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1−26, Tables 1−3 and References.

Reporting Summary.

Supplementary Video 1

Flammability tests of the dry cotton ball.

Supplementary Video 2

Flammability tests of EG and the Zn(BF4)2/EG electrolyte.

Source data

Source data for Fig. 1.

Price and volatility, flammability characterization of the Zn(BF4)2/EG electrolyte, as well as the internal interaction within the Zn(BF4)2/EG electrolyte.

Source data for Fig. 2.

SEM, XRD, Raman and XPS results of the Zn foil soaked in the 4 m Zn(BF4)2/EG electrolyte and the reference aqueous ZnSO4 electrolyte.

Source data for Fig. 3.

Long-term cycling, CE tests and SEM and AFM images of the Zn anodes cycled in the 4 m Zn(BF4)2/EG electrolyte and the reference aqueous ZnSO4 electrolyte.

Source data for Fig. 4.

Tolerance of the 4 m Zn(BF4)2/EG electrolyte to a wide temperature range, and the performance of Zn anodes under harsh conditions in different electrolytes.

Source data for Fig. 5.

Room- and low-temperature performance of Zn//V2O5 full cells, and images of the cycled V2O5 cathodes and the cycled separators.

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Han, D., Cui, C., Zhang, K. et al. A non-flammable hydrous organic electrolyte for sustainable zinc batteries. Nat Sustain 5, 205–213 (2022). https://doi.org/10.1038/s41893-021-00800-9

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