Realizing the Potential of Micro-Phase Separated Block Copolymer Electrolytes: Ion Domain Connectivity Plays a Prominent Role in Ion Conduction
Authors: Arges Christopher George , Kambe Yu , Dolejsi Moshe , Wu Guangpeng , Segal-Peretz Tamar , Ren Jiaxing , Nealey Paul F. 
Published: February 2020

Single ion conducting polymer electrolyte membranes (PEMs) are found at the heart of many electrochemical devices (e.g., fuel cells, flow batteries, electrolyzers, electrodialysis, etc.).(1) The key requirements for such materials include high ionic conductivity, electron insulation, mechanical resilience, selectivity (i.e., high transference #), and chemical, thermal, and mechanical stability.(2, 3) Ionic conductivity is particularly important because it strongly influences the ohmic overpotential in the said electrochemical devices affecting device efficiency.(1, 4)

Block copolymer electrolytes represent an attractive set of PEM materials because their micro-phase architecture yields greater ion conduction over their random copolymer counterparts.(5-7) Furthermore, the block copolymer charateristic gives rise to a variety of morphological architectures, while engineering of the block copolymer’s self-assembly influences domain alignment.(8-12) However, there is lack of systematic studies correlating molecular level structural design to bulk material properties like ion transport.

In this work, a model lamellae-forming diblock copolymer electrolyte system was manipulated to examine the extent of ion domain connectivity on ion conduction.(13, 14) Careful control of the model system’s volume fraction gave diblock copolymer structures with slightly rich electrolyte domains or slightly rich hydrophobic domains. The slightly rich electrolyte domains had greater contiguous area fraction while simultaneously demonstrating fewer terminal defects. Having a contiguous area fraction from 0.95 to 1.0 resulted in a 2x improvement in ionic conductivity over a non-micro-phase separated block copolymer electrolyte or a micro-phase separated block copolymer electrolyte with poor connectivity. Incremental adjustment in the extent of connectivity revealed an exponential growth curve for ion conductivity as a function of contiguous area fraction. Furthermore, the benefits that a micro-phase separated block copolymer electrolyte affords in terms of ion conductivity were not realized when the block copolymer electrolyte had poor connectivity. The results of this work have far reaching implication into the rationale design of PEM materials based upon block copolymer designs. This talk will emphasize the importance of maximizing ion domain connectivity while taking great strides to minimize terminal defects to boost ion transport in PEM materials. This talk will close with future directions on how molecular level engineering of block copolymer electrolytes offer the potential to reveal how other structural features (e.g., tortuosity(15), grain boundaries(5), and counterion condensation) alter ion transport in PEM materials(16, 17).

1. H. Strathmann et al., Ion-Exchange Membranes in the Chemical Process Industry. Industrial & Engineering Chemistry Research
52, 10364-10379 (2013).

2. H. Strathmann, Ion-Exchange Membrane Separation Processes, Volume 9. Membrane Science and Technology (Elsevier Science, Amsterdam, The Netherlands, 2004), vol. 9.

3. T. Sata, Ion Exchange Membranes: Preparation, Characterization, Modification and Application. (Royal Society of Chemistry, Cambridge, UK, 2004).

4. A. Z. Weber, J. Newman, Modeling Transport in Polymer-Electrolyte Fuel Cells. Chemical Reviews
104, 4679-4726 (2004).

5. Y. A. Elabd, M. A. Hickner, Block Copolymers for Fuel Cells. Macromolecules
44, 1-11 (2011).

6. N. Li, M. D. Guiver, Ion Transport by Nanochannels in Ion-Containing Aromatic Copolymers. Macromolecules
47, 2175-2198 (2014).

7. Y. Schneider et al., Ionic Conduction in Nanostructured Membranes Based on Polymerized Protic Ionic Liquids. Macromolecules
46, 1543-1548 (2013).

8. H. Hu, M. Gopinadhan, C. O. Osuji, Directed self-assembly of block copolymers: a tutorial review of strategies for enabling nanotechnology with soft matter. Soft Matter
10, 3867-3889 (2014).

9. M. Luo, T. H. Epps, III, Directed Block Copolymer Thin Film Self-Assembly: Emerging Trends in Nanopattern Fabrication. Macromolecules
46, 7567-7579 (2013).

10. S. Ji, L. Wan, C.-C. Liu, P. F. Nealey, Directed self-assembly of block copolymers on chemical patterns: A platform for nanofabrication. Progress in Polymer Science, 54-55, 76-127 (2016).

11. S.-J. Jeong et al., Directed self-assembly of block copolymers for next generation nanolithography. Materials Today
16, 468-476 (2013).

12. M. P. Stoykovich, P. F. Nealey, Block copolymers and conventional lithography. Materials Today
9, 20-29 (2006).

13. I. P. Campbell, G. J. Lau, J. L. Feaver, M. P. Stoykovich, Network Connectivity and Long-Range Continuity of Lamellar Morphologies in Block Copolymer Thin Films. Macromolecules  45, 1587-1594 (2012).

14. C. G. Arges, Y. Kambe, H. S. Suh, L. E. Ocola, P. F. Nealey, Perpendicularly Aligned, Anion Conducting Nanochannels in Block Copolymer Electrolyte Films. Chemistry of Materials
28, 1377-1389 (2016).

15. X. Feng et al., Scalable Fabrication of Polymer Membranes with Vertically Aligned 1 nm Pores by Magnetic Field Directed Self-Assembly. ACS Nano
8, 11977-11986 (2014).

16. K. M. Beers, D. T. Hallinan, X. Wang, J. A. Pople, N. P. Balsara, Counterion Condensation in Nafion. Macromolecules
44, 8866-8870 (2011).

17. K. M. Beers, N. P. Balsara, Design of Cluster-free Polymer Electrolyte Membranes and Implications on Proton Conductivity. ACS Macro Letters
1, 1155-1160 (2012).

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