Article | Published:

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

Nature Energyvolume 3pages10761083 (2018) | Download Citation


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.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

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.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.


  1. 1.

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

  2. 2.

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

  3. 3.

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

  4. 4.

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

  5. 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).

  6. 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).

  7. 7.

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

  8. 8.

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

  9. 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).

  10. 10.

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

  11. 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).

  12. 12.

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

  13. 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).

  14. 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).

  15. 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).

  16. 16.

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

  17. 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).

  18. 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).

  19. 19.

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

  20. 20.

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

  21. 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).

  22. 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).

  23. 23.

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

  24. 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).

  25. 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).

  26. 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).

  27. 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).

  28. 28.

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

  29. 29.

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

  30. 30.

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

  31. 31.

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

  32. 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).

Download references


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.

Author information


  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


  1. Search for Guoxing Li in:

  2. Search for Zhe Liu in:

  3. Search for Qingquan Huang in:

  4. Search for Yue Gao in:

  5. Search for Michael Regula in:

  6. Search for Daiwei Wang in:

  7. Search for Long-Qing Chen in:

  8. Search for Donghai Wang in:


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.

Competing interests

The authors declare no competing interests

Corresponding author

Correspondence to Donghai Wang.

Supplementary information

  1. Supplementary Information

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

  2. 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

  3. 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

  4. 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

About this article

Publication history