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Regulating electrodeposition morphology in high-capacity aluminium and zinc battery anodes using interfacial metal–substrate bonding

Nature Energy volume 6, pages 398–406 (2021)Cite this article

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Abstract

Although Li-based batteries have established a dominant role in the current energy-storage landscape, post-Li chemistries (for example, Al or Zn) are emerging as promising candidates for next-generation rechargeable batteries. Electrochemical cells using Al or Zn metal as the negative electrode are of interest for their potential low cost, intrinsic safety and sustainability. Presently, such cells are considered impractical because the reversibility of the metal anode is poor and the amount of charge stored is miniscule. Here we report that electrodes designed to promote strong oxygen-mediated chemical bonding between Al deposits and the substrate enable a fine control of deposition morphology and provide exceptional reversibility (99.6–99.8%). The reversibility is sustained over unusually long cycling times (>3,600 hours) and at areal capacities up to two orders of magnitude higher than previously reported values. We show that these traits result from the elimination of fragile electron transport pathways, and the non-planar deposition of Al via specific metal–substrate chemical bonding.

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Fig. 1: Metal–substrate bonding-induced regulation of electrodeposition.
Fig. 2: The propensity of Al anodes to exhibit heterogeneous growth on conventional substrates.
Fig. 3: Microstructure of Al metal deposits formed on a substrate with strong metal–substrate bonding.
Fig. 4: XPS characterization of the metal–substrate interaction.
Fig. 5: Electrochemical cycling behaviour of structured Al electrodes in galvanostatic plating/stripping experiments.
Fig. 6: Ultrahigh current density plating/stripping of Al.

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Data availability

The datasets generated during the current study are available in the article and its Supplementary Information.

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Acknowledgements

We thank F. Zhu, L. Luo, R. Luo, M. Pfeifer and X. Ren for valuable discussions. This work was supported as part of the Center for Mesoscale Transport Properties, an Energy Frontier Research Center supported by the US Department of Energy, Office of Science, Basic Energy Sciences, under award no. DE-SC0012673. This work made use of the Cornell Center for Materials Research Shared Facilities which are supported through the NSF MRSEC program (DMR-1719875). The pouch cell assembly line used for the anode-free electrodes with a 9 cm2 area was supported under award 75039 from the New York State Energy Research and Development Authority (NYSERDA) and award 76890 from the New York State Department of Economic Development (DED), which were provided as matching funds to the Center for Mesoscale Transport Properties under award no. DE-SC0012673. E.S.T. acknowledges support as the William and Jane Knapp Chair of Energy and the Environment.

Author information

Authors and Affiliations

  1. Department of Materials Science and Engineering, Cornell University, Ithaca, NY, USA

    Jingxu Zheng, Tian Tang, Yue Deng & Lynden A. Archer

  2. Energy and Photon Sciences Directorate, Brookhaven National Laboratory, Upton, NY, USA

    David C. Bock, Killian R. Tallman, Garrett Wheeler, Amy C. Marschilok & Esther S. Takeuchi

  3. Robert Frederick Smith School of Chemical and Biomolecular Engineering, Cornell University, NY, USA

    Qing Zhao, Jiefu Yin, Xiaotun Liu, Shuo Jin & Lynden A. Archer

  4. Department of Chemistry, State University of New York at Stony Brook, Stony Brook, NY, USA

    Amy C. Marschilok, Esther S. Takeuchi & Kenneth J. Takeuchi

  5. Department of Materials Science and Chemical Engineering, State University of New York at Stony Brook, Stony Brook, NY, USA

    Amy C. Marschilok, Esther S. Takeuchi & Kenneth J. Takeuchi

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  1. Jingxu Zheng
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Contributions

L.A.A. directed the research. J.Z. and L.A.A. conceived and designed this work. J.Z. and L.A.A. wrote the paper with inputs from other authors. J.Z. and T.T. performed the electrodeposition, electrochemical measurements and structure characterizations. J.Z., Q.Z., G.W. and D.C.B. assembled the pouch cells. D.C.B. and K.R.T. collected and interpreted the XPS data with input from A.C.M.; Q.Z., J.Y., X.L., Y.D. and J.S. analysed the data. All the authors contributed to the review and editing of the manuscript.

Corresponding author

Correspondence to Lynden A. Archer.

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Extended data

Extended Data Fig. 1 Electrochemical plating/stripping behavior of Al metal on nonplanar nickel foam substrate.

a, Coulombic efficiency obtained at 0.8 mAh, 4 mA/cm2. Voltage profiles of Al plating/stripping: (b) 0.8 mAh, 4 mA/cm2;(c) 3.2 mAh, 1.6 mAh/cm2 and (d) 8.0 mAh, 1.6 mA/cm2. The results mean that the improvement made by using a nonplanar, inert architecture is very limited, particularly at practical capacities, that is 3.2 and 8 mAh/cm2.

Extended Data Fig. 2 XPS spectrum of interwoven carbon fibers.

a, Pristine, (b) after exposure to IL+AlCl3 electrolyte, (c) after exposure to dimethyl carbonate as a negative control. Peak assignments: 284.8 eV (C-C, C-H), 286 eV (C-O), 287.5–288 eV (C=O, O-C-O), 289 eV (O=C-O). The intensities at 286 and 287.5 ~ 288 eV suggest that the exposure to IL+AlCl3 notably increases the level of oxygen enrichment on carbon fibers.

Extended Data Fig. 3 SEM images and EDS mapping of Al deposition morphology obtained using a sequential, two-step protocol.

In Step I, a small capacity (0.05 mAh/cm2) of Al is deposited at fixed overpotential, η values (for example, η = 0.05, 0.3, 1.0, 2.0, 3.0 V); In Step II, a greater areal capacity (that is 0.45 mAh/cm2) of Al is galvanostatically deposited at a current density (that is 4 mA/cm2). SEM images of the Al deposition morphology obtained using this protocol, with the η value equal to (a) 0.05 V, (b) 0.3 V, (c) 1.0 V, (d) 2.0 V, and (e) 3.0 V. f–o, the corresponding EDS mapping results. See Supplementary Note 1 for a detailed discussion.

Extended Data Fig. 4. XPS spectrum of Al electrodeposits on carbon fibers, stainless steel and nickel foam.

XPS of Al deposited on (a)–(c) carbon fibers, (d)–(f) stainless steel, and (g)–(i) Ni foam. (a)(d)(g) C 1 s spectra; (b)(e)(h) O 1 s spectra; (c)(f)(i) Al 2p spectra. Upper panels and lower panels show spectra before and after Ar+ sputtering, respectively. After sputtering, the Al-O-C bonding was observed on samples where Al was deposited on carbon fibers. On other samples, no characteristic metal-substrate covalent bonding is observable.

Supplementary information

Supplementary Information

Supplementary Tables 1 and 2, Supplementary Note 1, and Supplementary Figures 1–20.

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Zheng, J., Bock, D.C., Tang, T. et al. Regulating electrodeposition morphology in high-capacity aluminium and zinc battery anodes using interfacial metal–substrate bonding. Nat Energy 6, 398–406 (2021). https://doi.org/10.1038/s41560-021-00797-7

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