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Electrostatic control of block copolymer morphology

Nature Materials volume 13, pages 694–698 (2014)Cite this article

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Abstract

Energy storage is at present one of the foremost issues society faces. However, material challenges now serve as bottlenecks in technological progress1. Lithium-ion batteries are the current gold standard to meet energy storage needs; however, they are limited owing to the inherent instability of liquid electrolytes1,2. Block copolymers can self-assemble into nanostructures that simultaneously facilitate ion transport and provide mechanical stability. The ions themselves have a profound, yet previously unpredictable, effect on how these nanostructures assemble and thus the efficiency of ion transport3. Here we demonstrate that varying the charge of a block copolymer is a powerful mechanism to predictably tune nanostructures. In particular, we demonstrate that highly asymmetric charge cohesion effects can induce the formation of nanostructures that are inaccessible to conventional uncharged block copolymers, including percolated phases desired for ion transport. This vastly expands the design space for block copolymer materials and is informative for the versatile design of battery electrolyte materials.

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Figure 1: Schematic of block copolyelectrolytes and discussion of neutral block copolymers and charge solubility effects.
Figure 2: Effect of charge cohesion on nanostructure phase behaviour.
Figure 3: Charge control of percolating nanostructures.
Figure 4: Effect of charge fraction on nanostructure phase behaviour.

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Acknowledgements

The authors acknowledge support from NSF grant number DMR-1309027. C.E.S. thanks the Northwestern International Institute for Nanotechnology for an International Institute for Nanotechnology Postdoctoral Fellowship, J. McGinnis for helpful comments on the manuscript, and A. F. Hannon for help with three-dimensional block copolymer visualization. The computational cluster is funded by the Office of the Director of Defense Research and Engineering (DDR&E) and the Air Force Office of Scientific Research (AFOSR) under Award no. FA9551-10-1-0167.

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  1. Department of Materials Science, Northwestern University, 2220 Campus Drive, Evanston, Illinois 60208, USA

    Charles E. Sing, Jos W. Zwanikken & Monica Olvera de la Cruz

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  1. Charles E. Sing
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  3. Monica Olvera de la Cruz
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Contributions

C.E.S., J.W.Z. and M.O.C. designed the research. C.E.S. and J.W.Z. developed the theoretical methods with input from M.O.C. C.E.S. performed the calculations. All authors contributed to the interpretation of the data and wrote the manuscript.

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Correspondence to Monica Olvera de la Cruz.

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The authors declare no competing financial interests.

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Sing, C., Zwanikken, J. & Olvera de la Cruz, M. Electrostatic control of block copolymer morphology. Nature Mater 13, 694–698 (2014). https://doi.org/10.1038/nmat4001

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