Abstract
Aqueous zinc-metal batteries are plagued by poor Zn reversibility owing to zinc dendrite and layered double hydroxide (LDH) formation. Here, we introduce a novel additive—N,N-dimethylformamidium trifluoromethanesulfonate (DOTf)—in a low-cost aqueous electrolyte that can very effectively address these issues. The initial water-assisted dissociation of DOTf into triflic superacid creates a robust nanostructured solid-electrolyte interface (SEI)—revealed by operando spectroscopy and cryomicroscopy—which excludes water and enables dense Zn deposition. We demonstrate excellent Zn plating/stripping in a Zn||Cu asymmetric cell for more than 3,500 cycles. Furthermore, near 100% CE is realized at a combined high current density of 4 mA cm−2 and an areal capacity of 4 mAh cm−2 over long-term cycling. Zn||Zn0.25V2O5·nH2O full cells retain ∼83% of their capacity after 1,000 cycles with mass-limited Zn anodes. By restricting the depth of discharge, the cathodes exhibit less proton intercalation and LDH formation with an extended lifetime of 2,000 cycles.
| Original language | English |
|---|---|
| Pages (from-to) | 1103-1120 |
| Number of pages | 18 |
| Journal | Joule |
| Volume | 6 |
| Issue number | 5 |
| DOIs | |
| State | Published - May 18 2022 |
| Externally published | Yes |
Funding
This work was financially supported by the Joint Centre for Energy Storage Research , an Energy Innovation Hub funded by the US Department of Energy , Office of Science , Basic Energy Sciences . This work was performed, in part, at the Center for Integrated Nanotechnologies (CINT), an Office of Science User Facility operated for the US Department of Energy (DOE), Office of Science. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia , LLC , a wholly owned subsidiary of Honeywell International, Inc. , for the US DOE ’s National Nuclear Security Administration under contract DE-NA0003525 . This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the US Department of Energy or the United States Government. We would like to thank L. Zhou (University of Waterloo) for helpful discussions and P. Broderson (University of Toronto) for carrying out the XPS experiments. L.F.N also acknowledges NSERC for platform support through the Discovery Grant and Canada Research Chair programs . This work was financially supported by the Joint Centre for Energy Storage Research, an Energy Innovation Hub funded by the US Department of Energy, Office of Science, Basic Energy Sciences. This work was performed, in part, at the Center for Integrated Nanotechnologies (CINT), an Office of Science User Facility operated for the US Department of Energy (DOE), Office of Science. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International, Inc., for the US DOE's National Nuclear Security Administration under contract DE-NA0003525. This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the US Department of Energy or the United States Government. We would like to thank L. Zhou (University of Waterloo) for helpful discussions and P. Broderson (University of Toronto) for carrying out the XPS experiments. L.F.N also acknowledges NSERC for platform support through the Discovery Grant and Canada Research Chair programs. C.L. and L.F.N. designed this study. C.L. synthesized the materials and carried out the characterization and all the electrochemical measurements. A.S. performed NMR measurement. A.G.H. and A.A.G. carried out the SEIRAS. C.Y.K. helped with XPS experiments and data analysis. D.M.L. P.G.K. and K.R.Z. conduced TEM measurements. C.L. and L.F.N. wrote the manuscript with contributions from A.G.H. A.A.G. D.M.L. and K.R.Z. The authors declare no competing interests.
Keywords
- SEIRAS
- Superacid
- XPS
- Zn anode
- Zn metal batteries
- Zn-ion batteries
- cryo-TEM
