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Stable metal battery anodes enabled by polyethylenimine sponge hosts by way of electrokinetic effects

Abstract

The cycle life and energy density of rechargeable metal batteries are largely limited by the dendritic growth of their metal anodes (lithium, sodium or zinc). Here we develop a three-dimensional cross-linked polyethylenimine lithium-ion-affinity sponge as the lithium metal anode host to mitigate the problem. We show that electrokinetic surface conduction and electro-osmosis within the high-zeta-potential sponge change the concentration and current density profiles, which enables dendrite-free plating/stripping of lithium with a high Coulombic efficiency at high deposition capacities and current densities, even at low temperatures. The use of a lithium-hosting sponge leads to a significantly improved cycling stability of lithium metal batteries with a limited amount of lithium (for example, the areal lithium ratio of negative to positive electrodes is 0.6) at a commercial-level areal capacity. We also observed dendrite-free morphology in sodium and zinc anodes, which indicates a broader promise of this approach.

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Fig. 1: The 3D PPS metal host.
Fig. 2: The Li-ion electrokinetic self-concentrating and pumping features of the 3D PPS.
Fig. 3: Morphology evolution of the Li deposited on the 3D PPS@Cu.
Fig. 4: 2D phase-field simulation of Li deposition on 3D PPS@Cu and bare Cu electrodes.
Fig. 5: The morphology of Li metal deposited on the different electrodes.
Fig. 6: Cycling stability of Li plating/stripping of 3D PPS@Cu electrodes and electrochemical performance of full cells using 3D PPS@Cu with limited Li as the anodes and LiFePO4 as the cathodes.

Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.

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Acknowledgements

This material is based on work supported by the Department of Energy, Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technology Office, under Award no. DE-EE0007795 (experimental work) and DE-EE0007803 (modelling work). The authors appreciate T. Stecko at The Pennsylvania State University for the analysis of MCT data.

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Authors

Contributions

G.L. and Do.W. conceived and designed the experiments. G.L. performed the laboratory experiments, characterization of materials and analysis of the results. Z.L. performed the simulation. Z.L. and L.C. proposed the explanation for the simulation. Y.G. performed the XPS measurements. G.L. and Do.W. prepared the manuscript and all the authors discussed the results and commented on the manuscript.

Corresponding author

Correspondence to Donghai Wang.

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The authors declare no competing interests

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Supplementary information

Supplementary Information

Supplementary Figures 1–40, Supplementary Tables 1–3, Supplementary Notes 1–2, Supplementary References

Supplementary Video 1

The MCT data of 3D PPS shows that the pores in 3D PPS have a high interconnectivity. The interconnected pores account for 99.99% of the total pore volume. Red represents isolated pores and white represents sponge walls in the video. The free-standing and thick 3D PPS samples were prepared using the same experimental conditions with 3D PPS@Cu for the characterization

Supplementary Video 2

The electro-osmosis pumps the electrolyte to flow from negative to positive through the cross-linked branched PEI modified plastic microtube (inner diameter: 850 µm, length: 1.8 cm). The movie speed is quadrupled

Supplementary Video 3

The un-modified plastic microtube (inner diameter: 850 µm, length: 1.8 cm) cannot provide the electro-osmosis. The movie speed is quadrupled

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Li, G., Liu, Z., Huang, Q. et al. Stable metal battery anodes enabled by polyethylenimine sponge hosts by way of electrokinetic effects. Nat Energy 3, 1076–1083 (2018). https://doi.org/10.1038/s41560-018-0276-z

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