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Fluorinated interphase enables reversible aqueous zinc battery chemistries

Nature Nanotechnology volume 16, pages 902–910 (2021)Cite this article

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Abstract

Metallic zinc is an ideal anode due to its high theoretical capacity (820 mAh g−1), low redox potential (−0.762 V versus the standard hydrogen electrode), high abundance and low toxicity. When used in aqueous electrolyte, it also brings intrinsic safety, but suffers from severe irreversibility. This is best exemplified by low coulombic efficiency, dendrite growth and water consumption. This is thought to be due to severe hydrogen evolution during zinc plating and stripping, hitherto making the in-situ formation of a solid–electrolyte interphase (SEI) impossible. Here, we report an aqueous zinc battery in which a dilute and acidic aqueous electrolyte with an alkylammonium salt additive assists the formation of a robust, Zn2+-conducting and waterproof SEI. The presence of this SEI enables excellent performance: dendrite-free zinc plating/stripping at 99.9% coulombic efficiency in a Ti||Zn asymmetric cell for 1,000 cycles; steady charge–discharge in a Zn||Zn symmetric cell for 6,000 cycles (6,000 h); and high energy densities (136 Wh kg−1 in a Zn||VOPO4 full battery with 88.7% retention for >6,000 cycles, 325 Wh kg−1 in a Zn||O2 full battery for >300 cycles and 218 Wh kg−1 in a Zn||MnO2 full battery with 88.5% retention for 1,000 cycles) using limited zinc. The SEI-forming electrolyte also allows the reversible operation of an anode-free pouch cell of Ti||ZnxVOPO4 at 100% depth of discharge for 100 cycles, thus establishing aqueous zinc batteries as viable cell systems for practical applications.

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Fig. 1: Electrochemical properties of different electrolytes.
Fig. 2: SEM and TEM imaging of Zn metal after 50 plating/stripping cycles in different electrolytes in a Zn||Zn symmetric cell at 0.5 mA cm−2 and 0.25 mAh cm−2.
Fig. 3: XPS spectra of F1s and C1s for Zn metal after 50 plating/stripping cycles in 4 m Zn(OTF)2 + 0.5 m Me3EtNOTF at a current density of 0.5 mA cm−2.
Fig. 4: Proposed mechanism demonstrating synergistic reactions between triflate and trimethylethyl ammonium to deposit predominantly fluoride and carbonate-based SEI.
Fig. 5: Electrochemical performances of Zn–oxygen and Zn-ion batteries.
Fig. 6: Fabrication and electrochemical performances of aritificial ZnF2 SEI.

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Data availability

The data that support the findings of this study are available from the corresponding authors upon reasonable request.

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Acknowledgements

C.W. acknowledges funding support from the US Department of Energy (DOE) through ARPA-E grant DEAR0000389 and the Center of Research on Extreme Batteries. Modelling and experimental work at Army Research Laboratory was supported by the Joint Center for Energy Storage Research, an Energy Innovation Hub funded by the US Department of Energy under cooperative agreement no. W911NF-19-2-0046. E.H. and X.-Q.Y. are supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technology Office of the US DOE through the Advanced Battery Materials Research Program under contract no. DE-SC0012704. This research used beamline 7-BM of the National Synchrotron Light Source II, a US DOE Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under contract no. DESC0012704.

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  1. These authors contributed equally: Longsheng Cao, Dan Li, Travis Pollard.

Authors and Affiliations

  1. Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, MD, USA

    Longsheng Cao, Dan Li, Tao Deng, Bao Zhang, Chongyin Yang, Long Chen, Lin Ma, Qin Li, Singyuk Hou, Karen Gaskell & Chunsheng Wang

  2. Battery Science Branch, Energy Science Division, Sensor and Electron Devices Directorate, US Army Research Laboratory, Adelphi, MD, USA

    Travis Pollard, Jenel Vatamanu, Lin Ma, Michael Ding, Kang Xu & Oleg Borodin

  3. Chemistry Division, Brookhaven National Laboratory, Upton, NY, USA

    Enyuan Hu & Xiao-Qing Yang

  4. Department of Chemistry and Biochemistry, University of Maryland, College Park, MD, USA

    Matt J. Hourwitz, John T. Fourkas & Chunsheng Wang

  5. Institute for Physical Science and Technology, University of Maryland, College Park, MD, USA

    John T. Fourkas

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Contributions

L. Cao and D.L. designed the experiments and analysed data. K.X. synthesized the asymmetric ammonium salt. T.P., O.B. and J.V. conducted the calculations. T.D., C.Y., L. Chen, L.M., Q.L. and S.H. assisted with the material synthesis and characterizations. E.H. and X.-Q.Y. did X-ray absorption spectroscopy measurement and data analysis. M.D. performed conductivity and differential scanning calorimetry measurements. K.G. assisted with XPS analysis. M.J.H. and J.T.F. assisted with contact-angle testing. K.X., O.B. and C.W. conceived and supervised the project. All authors contributed to interpretation of the results.

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Correspondence to Kang Xu, Oleg Borodin or Chunsheng Wang.

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Supplementary Figs. 1–46, Tables 1–5 and notes 1–2.

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Cao, L., Li, D., Pollard, T. et al. Fluorinated interphase enables reversible aqueous zinc battery chemistries. Nat. Nanotechnol. 16, 902–910 (2021). https://doi.org/10.1038/s41565-021-00905-4

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