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Chloride electrolyte enabled practical zinc metal battery with a near-unity Coulombic efficiency

Nature Sustainability volume 6, pages 806–815 (2023)Cite this article

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Abstract

Rechargeable aqueous zinc batteries are finding their niche in stationary storage applications where safety, cost, scalability and carbon footprint matter most. However, harnessing this reversible two-electron redox chemistry is plagued by major technical issues, notably hydrogen evolution reaction (HER) at the zinc surface, whose impacts are often not revealed under typical measurement conditions. Here we report a concentrated electrolyte design that eliminates this parasitic reaction and enables a Coulombic efficiency (CE) of 99.95% for Zn plating/stripping measured at a low current density of 0.2 mA cm−2. With extra chloride salts and dimethyl carbonate in concentrated ZnCl2 electrolyte, the hybrid electrolyte with a unique chemical environment features low Hammett acidity and facilitates the in situ formation of a dual-layered solid electrolyte interphase, protecting zinc anodes from HER and dendrite growth. Benefiting from the near-unity CE, the pouch cell with a VOPO4·2H2O cathode sustains 500 deep cycles without swelling or leaking and delivers an energy density of 100 Wh kg−1 under practical conditions. Our work represents a critical step forward in accelerating the market adoption of zinc batteries as an energy storage system with higher sustainability.

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Fig. 1: Reversibility of ZMA and properties of the electrolytes.
Fig. 2: Physical characterization of ZMA in 30Z and ZLT-DMC electrolytes.
Fig. 3: Physical characterization of the interfacial chemistry of ZMA in ZLT-DMC.
Fig. 4: Electrochemical performance of VOPO4·2H2O||Zn full cells.

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Data availability

The data that support the findings of this study are available in the Article and its Supplementary Information.

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Acknowledgements

H.J. acknowledges the financial support from NSF SBIR-2012221. X.J., C.F., and P.A.G. thank the financial support from US NSF Award CBET-2038381 (X.J., C.F.) and CBET-2038366 (P.A.G.). J.L. acknowledges support as part of the Hydrogen in Energy and Information Sciences, an Energy Frontier Research Center funded by US DOE Award DE-SC0023450. This work made use of instruments in the Electron Microscopy Service and Nuclear Magnetic Resonance Facility (Oregon State University). X.J. thanks Dr. Peter Eschbach, Stephen Huhn, and Dr. Patrick Reardon for their instrument assistance.

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Authors and Affiliations

  1. Department of Chemistry, Oregon State University, Corvallis, OR, USA

    Heng Jiang, Longteng Tang, Sean K. Sandstrom, Alexis M. Scida, David Hoang, Jessica J. Hong, Nan-Chieh Chiu, Kyriakos C. Stylianou, Chong Fang & Xiulei Ji

  2. GROTTHUSS INC., Corvallis, Oregon, USA

    Heng Jiang & Xiulei Ji

  3. Department of Materials Science and Engineering, University of California, Riverside, CA, USA

    Yanke Fu & P. Alex Greaney

  4. Department of Nuclear Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA

    Shitong Wang & Ju Li

  5. Department of Mechanical Engineering, The Pennsylvania State University, University Park, PA, USA

    Guoxing Li & Donghai Wang

  6. Hewlett-Packard Co., Corvallis, OR, USA

    William F. Stickle

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  1. Heng Jiang
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Contributions

X.J. conceived the concept for the research. H.J. designed the experiments and analysed data with assistance from S.K.S., G.L., D.H. and J.J.H. GS-FSRS measurements were performed by L.T. under the guidance of C.F. P.A.G. supervised the AIMD simulation that Y.F. carried out. J.L. supervised the in situ optical microscopies that S.W. performed. D.H. and N.-C.C. performed the ultraviolet–visible spectroscopy and gas chromatography tests under the supervision of K.C.S. A.M.S. collected the nuclear magnetic resonance data, and W.F.S. conducted the X-ray photoelectron spectroscopy measurements. X.J., C.F., P.A.G., J.L. and D.W. supervised the project. All authors contributed to interpreting the results, discussed the data and reviewed the final draft.

Corresponding authors

Correspondence to P. Alex Greaney, Chong Fang or Xiulei Ji.

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Competing interests

X.J. and H.J. are inventors on US patent application no. 17/867,672 filed by GROTTHUSS INC. regarding the formula of the electrolytes described in this Article. The other authors declare no competing interests.

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Nature Sustainability thanks Longsheng Cao 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. 1–30, tables 1–4 and discussion.

Reporting summary.

In situ optical microscopy video of ZMA plating in ZLT-DMC.

In situ optical microscopy video of ZMA plating in 30Z-DMC.

In situ optical microscopy video of ZMA plating in ZLT.

In situ optical microscopy video of ZMA plating in ZL.

In situ optical microscopy video of ZMA plating in 30Z.

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Jiang, H., Tang, L., Fu, Y. et al. Chloride electrolyte enabled practical zinc metal battery with a near-unity Coulombic efficiency. Nat Sustain 6, 806–815 (2023). https://doi.org/10.1038/s41893-023-01092-x

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