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

Nature Energy volume 3, pages 1076–1083 (2018)Cite this article

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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.

References

  1. Kim, H. et al. Metallic anodes for next generation secondary batteries. Chem. Soc. Rev. 42, 9011–9034 (2013).

    Article  Google Scholar 

  2. Tarascon, J. M. & Armand, M. Issues and challenges facing rechargeable lithium batteries. Nature 414, 359–367 (2001).

    Article  Google Scholar 

  3. Xu, K. Nonaqueous liquid electrolytes for lithium-based rechargeable batteries. Chem. Rev. 104, 4303–4417 (2004).

    Article  Google Scholar 

  4. Xu, W. et al. Lithium metal anodes for rechargeable batteries. Energy Environ. Sci. 7, 513–537 (2014).

    Article  Google Scholar 

  5. Liu, Y. Y. et al. An artificial solid electrolyte interphase with high Li-ion conductivity, mechanical strength, and flexibility for stable lithium metal anodes. Adv. Mater. 29, 1605531 (2017).

    Article  Google Scholar 

  6. Zhu, B. et al. Poly(dimethylsiloxane) thin film as a stable interfacial layer for high-performance lithium-metal battery anodes. Adv. Mater. 29, 1603755 (2017).

    Article  Google Scholar 

  7. Zheng, G. et al. Interconnected hollow carbon nanospheres for stable lithium metal anodes. Nat. Nanotech. 9, 618–623 (2014).

    Article  Google Scholar 

  8. Liang, X. et al. A facile surface chemistry route to a stabilized lithium metal anode. Nat. Energy 2, 17119 (2017).

    Article  Google Scholar 

  9. Li, G. X. et al. Organosulfide-plasticized solid-electrolyte interphase layer enables stable lithium metal anodes for long-cycle lithium-sulfur batteries. Nat. Commun. 8, 850 (2017).

    Article  Google Scholar 

  10. Zheng, J. M. et al. Electrolyte additive enabled fast charging and stable cycling lithium metal batteries. Nat. Energy 2, 17012 (2017).

    Article  Google Scholar 

  11. Li, G. X. et al. Self-formed hybrid interphase layer on lithium metal for high-performance lithium-sulfur batteries. ACS Nano 12, 1500–1507 (2018).

    Article  Google Scholar 

  12. Qian, J. et al. High rate and stable cycling of lithium metal anode. Nat. Commun. 6, 6362 (2015).

    Article  Google Scholar 

  13. Suo, L. M. et al. A new class of solvent-in-salt electrolyte for high-energy rechargeable metallic lithium batteries. Nat. Commun. 4, 1481 (2013).

    Article  Google Scholar 

  14. Fan, L. et al. Stable lithium electrodeposition at ultra-high current densities enabled by 3D PMF/Li composite anode. Adv. Energy Mater. 8, 1703360 (2018).

    Article  Google Scholar 

  15. Cheng, X.-B. et al. Dendrite-free lithium deposition induced by uniformly distributed lithium ions for efficient lithium metal batteries. Adv. Mater. 28, 2888–2895 (2016).

    Article  Google Scholar 

  16. Liang, Z. et al. Polymer nanofiber-guided uniform lithium deposition for battery electrodes. Nano. Lett. 15, 2910–2916 (2015).

    Article  Google Scholar 

  17. Lin, D. et al. Layered reduced graphene oxide with nanoscale interlayer gaps as a stable host for lithium metal anodes. Nat. Nanotech. 11, 626–632 (2016).

    Article  Google Scholar 

  18. Liu, Y. Y. et al. Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode. Nat. Commun. 7, 10992 (2016).

    Article  Google Scholar 

  19. Brady, R. M. & Ball, R. C. Fractal growth of copper electrodeposits. Nature 309, 225–229 (1984).

    Article  Google Scholar 

  20. Bazant, M. Z. Regulation of ramified electrochemical growth by a diffusive wave. Phys. Rev. E 52, 1903–1914 (1995).

    Article  Google Scholar 

  21. Sand, H. J. S. III. On the concentration at the electrodes in a solution, with special reference to the liberation of hydrogen by electrolysis of a mixture of copper sulphate and sulphuric acid. Philos. Mag. 1, 45–79 (1901).

    Article  Google Scholar 

  22. Yang, C.-P. et al. Accommodating lithium into 3D current collectors with a submicron skeleton towards long-life lithium metal anodes. Nat. Commun. 6, 8058 (2015).

    Article  Google Scholar 

  23. Yun, Q. B. et al. Chemical dealloying derived 3D porous current collector for Li metal anodes. Adv. Mater. 28, 6932–6939 (2016).

    Article  Google Scholar 

  24. Ye, H. et al. Stable Li plating/stripping electrochemistry realized by a hybrid Li reservoir in spherical carbon granules with 3D conducting skeletons. J. Am. Chem. Soc. 139, 5916–5922 (2017).

    Article  Google Scholar 

  25. Zuo, T. T. et al. Graphitized carbon fibers as multifunctional 3D current collectors for high areal capacity Li anodes. Adv. Mater. 29, 1700389 (2017).

    Article  Google Scholar 

  26. Stone, H. A., Stroock, A. D. & Ajdari, A. Engineering flows in small devices: microfluidics toward a lab-on-a-chip. Annu. Rev. Fluid Mech. 36, 381–411 (2004).

    Article  Google Scholar 

  27. Dydek, E. V. & Bazant, M. Z. Nonlinear dynamics of ion concentration polarization in porous media: the leaky membrane model. AIChE J. 59, 3539–3555 (2013).

    Article  Google Scholar 

  28. Dydek, E. V. et al. Overlimiting current in a microchannel. Phys. Rev. Lett. 107, 118301 (2011).

    Article  Google Scholar 

  29. Delgado, A. V. et al. Measurement and interpretation of electrokinetic phenomena. J. Colloid Interf. Sci. 309, 194–224 (2007).

    Article  Google Scholar 

  30. Chatterjee, S., Sen Gupta, S. & Kumaraswamy, G. Omniphilic polymeric sponges by ice templating. Chem. Mater. 28, 1823–1831 (2016).

    Article  Google Scholar 

  31. Rajamanickam, R. et al. Soft colloidal scaffolds capable of elastic recovery after large compressive strains. Chem. Mater. 26, 5161–5168 (2014).

    Article  Google Scholar 

  32. Buhai, B., Binser, T. & Kimmich, R. Electroosmotic flow, ionic currents, and pressure-induced flow in microsystem channel networks: NMR mapping and computational fluid dynamics simulations. Appl. Magn. Reson. 32, 25–49 (2007).

    Article  Google Scholar 

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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 and Affiliations

  1. Department of Mechanical and Nuclear Engineering, The Pennsylvania State University, University Park, PA, USA

    Guoxing Li, Daiwei Wang & Donghai Wang

  2. Department of Materials Science and Engineering, The Pennsylvania State University, University Park, PA, USA

    Zhe Liu, Qingquan Huang & Long-Qing Chen

  3. Department of Chemistry, The Pennsylvania State University, University Park, PA, USA

    Yue Gao

  4. Department of Chemical Engineering, The Pennsylvania State University, University Park, PA, USA

    Michael Regula

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  1. Guoxing Li
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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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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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