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Mechanisms of Ionic Transport in Membranes for Batteries and Fuel Cells

Published online by Cambridge University Press:  01 February 2011

J. Woods Halley
Affiliation:
woods@jwhp.spa.umn.edu, University of Minnesota, Physics, Minneapolis, Minnesota, United States
Lingling Jia
Affiliation:
jialingling@gmail.com, University of Minnesota, Physics, Minneapolis, Minnesota, United States
Sean Bowman
Affiliation:
bowma166@umn.edu, University of Minnesota, Physics, Minneapolis, Minnesota, United States
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Abstract

Ionic transport in electrolyte membranes limits performance in both battery and fuel cell membranes. The problems have been well known for years, sometimes decades, but empirical progress in solving them has been slow. The focus here is on studies to improve understanding of transport mechanisms, which despite extensive study, remain in dispute in several important cases. For lithium transport in polymer membranes, I will review simulation work by ourselves and others, and contend that the original qualitative picture by Ratner and coworkers is confirmed in many respects by recent work. It means, however, that the fundamental difficulty is that the transport is controlled by torsion forces in the hydrocarbon backbone which are extremely difficult to manipulate experimentally. Turning to possibly promising additives, I review recent work on proton and lithium transport in ionic liquids, on which promising experimental results have been reported. The data, both from simulation and experiment, indicate nontrivial collective effects in the transport properties which need to be sorted out to control these systems. In the case of proton transport, we report results suggesting that high mobilities occur in acid-ionic mixtures with a common anion in mixtures near phase separation.

Type
Research Article
Copyright
Copyright © Materials Research Society 2010

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References

REFERENCES

1 Ohno, H., Washiro, S. and Yoshizawa, M, in “Ionic Liquids in Polymer Systems”, Brazel, S. and Rogers, R. D. eds. , American Chemical Society, Washington D. C. (2005) p. 89 Google Scholar
2 Shin, J. H., Henderson, W. A. and Passerini, S., “PEO-based polymer electrolytes with ionic liquids and their use in lithium metal-polymer electrolyte batteriesJ. Electrochem. Soc. 152, A978 (2005)Google Scholar
3 Henderson, W. A. and Passerini, S., “Phase behavior of ionic liquid-LiXmixtures: Pyrrolidinium cations and TFSI- anions”, Chem. Matt 16, 2881 (2004)Google Scholar
4 Castriota, M., Caruso, T.,Agostino, R. G., Cazzanelli, E., Henderson, W., and Passerini, S., “Raman investigation of the ionic liquid N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide and its mixture with LiN(SO2 CF3)2 ”, Journal of Physical Chemistry A 109, 9296 (2005)Google Scholar
5 Shin, J. H., Henderson, W. A. and Passerini, S., “An elegantfix for polymer electrolytesElectrochemical and Solid State Letters 8, A125–A127 (2005)Google Scholar
6 Jia, Lingling, Nguyen, Dat, Halley, J. W., Pham, Phat, Lamanna, William and Hamrock, Steven, “Proton Transport in HTFSI-EMI-TFSIMixtures: Experiment and Theory”, Journ. of the Electrochemical Society 156(1) B136–B151Google Scholar
7 Boden, N., Leng, S. A., Ward, I. M., “Ionic conductivity and diffusivity n polyethylene oxide/electrolyte solutions as models for polymer electrolytesSolid State Ionics 45, 261 (1991)Google Scholar
8 Ratner, M. in Polymer Electrolyte Reviews Vol. 1 ed. MacCallum, J. R and Vincent, C. A., Elsevier, London 1987 p. 173 Google Scholar
9 Gray, F. M., Solid Polymer Electrolytes (VCH Pub. NY, 1991)Google Scholar
10 Muller-Plathe, F., “Permeation of polymers- a computational approachActa Polymerica 45(4), 259(1994)Google Scholar
11 Mckechnie, J.I., Brown, D. and Clarke, J.H.R., “Methods of generating dense relaxed amorphous polymer samples for use in dynamic simulationsMacromolecules, 25, 1562 (1992).Google Scholar
12 Brown, D., Clarke, J.H.R., Okuda, M. and Yamazaki, T., J. Chem. Phys.Preparation of polymer melt samples for computer simulation studies100, 6011 (1994).}Google Scholar
13 Neyertz, S. and Brown, D., “Computer simulation study of the chain configurations in poly(ethylene oxide)-homolog meltsJ. Chem. Phys. 102, 9725 (1995).Google Scholar
14 Catlow, C.R.A., and Mills, G.E., “Computer simulation of ionically conducting polymersElectrochimica Acta 40, 2057 (1995).Google Scholar
15 Neyertz, S., Brown, D. and Thomas, J. O., Computational Polymer Science 5, 107120, (1995).Google Scholar
16 Neyertz, S. and Brown, D., ”Local structure and mobility of ions in polymer electrolytes: a molecular dynamics simulation study of the amorphous PEOxNal system”, Journal of Chemical Physics 104, 37973809 (1996).Google Scholar
17 Annis, B. K., Kim, M.-H., Wignall, G. D., Borodin, O. and Smith, G. D., “Study of the influence of LiI on the chain conformations of poly(ethyleneoxide) in the melt by smallangle neutron scattering and molecular dynamics simulationsMacromolecules 33, 75447548, (2000).Google Scholar
18 Borodin, O., “Force field development and MD simulations of poly(ethylene oxide)/LiBF4 polymer electrolytesJournal of Physical Chemistry B 107 (28): 68246837 (2003)Google Scholar
19 van, A. Zon, Bel, G. J., Mos, B., Verkerk, P. and Leeuw, S. W. De, “Structural relaxation inpoly(ethylene oxide)-salt solutionsComputational materials Science 17, 265268,(2000).Google Scholar
20 Mos, B., Verkerk, P., Pouget, S., Zon, A. van, Bel, G. J., Leeuw, S. W. de and Eisenbach, C. D., “Dynamics in polyethyleneoxide-alkali iodide complexes investigated by neutron spin-echo spectroscopy and molecular dynamics simulations”, The Journal of chemical physics 113, 47,(2000).Google Scholar
21 Borodin, O. and Smith, G. D., “Molecular dynamics simulations of poly(ethylene) oxide LiI melts. 2. Dynamic properties”, Macromolecules 33, 22732283, (2000)Google Scholar
22 Ennari, J., Neelov, I. and Sundholm, F., “Molecular dynamics simulation of the structure of PEO based solid polymer electrolytesPolymer Guildford 41, 40574063, (2000).Google Scholar
23 Ennari, J., Neelov, I. and Sundholm, F., “Simulation of a PEO based solid polyelectrolyte, comparison of the CMM and the Ewald summation methodPolymer Guildford 41, 21492155, (2000).Google Scholar
24 Borodin, O. and Smith, G. D., “Molecular dynamics simulations of poly(ethylene oxide)/LiI melts. 1. Structural and conformational properties”, Macromolecules 31, 83968406, (1998).Google Scholar
25 Lin, B.. Boinske, P. T. and Halley, J. W., ”Molecular dynamics model of the amorphous regions of polyethylene oxideJournal of Chemical Physics 105, (1996)Google Scholar
26 Halley, J. W., Duan, Yuhua, Nielsen, B., Redfern, Paul C., and Curtiss, Larry A., “Simulation of polyethylene oxide: Improved structure using better models for hydrogen and flexible walls”, Journal of Chemical Physics 115, 3957 (2001)Google Scholar
27 Johnson, J., Saboungi, M-L., Price, D. L., Ansell, S., Russell, T. P., Halley, J. W. and Nielsen, B., “Atomic structure of solid and liquid polyethylene oxideJournal of Chemical Physics 109, 7005(1998)Google Scholar
28 Halley, J. W., Duan, Y., Curtiss, L. A. and Baboul, A. G., “Lithium perchlorate ion pairing in a model of amorphous polyethylene oxide”, J. Chem. Phys. 111, 3302 (1999)Google Scholar
29 Duan, Yuhua, Halley, J. W., Curtiss, Larry, Redfern, Paul, “Mechanisms of lithium transport in amorphous polyethylene oxideJ. Chem. Physics 122, 54702 (2005)Google Scholar
30 Diddens, D., Heuer, A., Borodin, O., Macrocules 43, 2028 (2010)Google Scholar
31 Ishikawa, Masashi, Sugimoto, Toshinori, Kikuta, Manabu, Ishiko, Eriko and Kono, Michiyuki, Journal of Power Sources 162, 658 (2006)Google Scholar
32 Ma, Y.-L., Wainright, J. S., Litt, M. H., Savinell, R. F., Journal of the Electrochemical Society 151, A8 (2004)Google Scholar
33 Williams, M. V., Kunz, H. R., Fenton, J. M., Journal of Power Sources 135, 122(2004)Google Scholar
34 Masten, D. A., Bosco, A. D., Handbook of Fuel Cells:Fundamentals, Technology and Applications, Vol 4, Vielstien, W., Gasteiger, H. A., Lamm, A., Eds. John Wiley sol;& Sons: West Sussex, UK, 714724 (2003)Google Scholar
35 Hamrock, Steven J. and Yandrasits, Michael A. ,Polymer Reviews 46, 219 244 (2006)Google Scholar
36 Paddison, S. J., Zawodzinski, T. A., “Molecular modeling of the pendant chainin Nafion”, Solid State Ionics 113–115, 333 (1998)Google Scholar
37 Eikerling, M., Paddison, S. J., Zawodzinski, T. A. Jr., “Molecular orbital calculations of proton dissociation and hydration ofvarious acidic moieties for fuel cell polymersJournal of New Materials for Electrochemical Systems 5, 15 (2002)Google Scholar
38 Yamamoto, S., Hyodo, S-A., “A computer simulation study of the mesoscopic structure of the polyelectrolyte membrane Nafion”, Polymer Journal, 35, 519 (2003)Google Scholar
39 Mologin, D. A., Khalatur, P. G., Khokhlov, A. R., “Structural organization of watercontaining Nafion: A cellular-automaton-based simulation”, Macromolecular Theory and Simulations 11, 587 (2002)Google Scholar
40 Hayashi, H., Yamamoto, S., , S., Hyodo, S.-A., “Lattice-Boltzmann simulations of flow through Nafion polymer membranesInternational Journal of Modern Physics B 17, 135 (2003)Google Scholar
41 Paddison, S. J., Paul, R., Zawodzinski, T. A., “Proton friction and diffusion coefficients in hydrated polymer electrolyte membranes: Computations with a non-equilibrium statistical mechanical modelJournal of Chemical Physics, 115, 7753 (2001)Google Scholar
42 Paddison, S. J., Paul, R., “The nature of proton transport in fully hydrated Nafion”, Physical Chemistry Chemical Physics 4, 1158, (2002)Google Scholar
43 Panday, Ashoutosh, Mullin, Scott, Gomez, Enrique. Wanakule, Nisita, Chen, Vincent L., Hesemer, Alexander, Pople, John and Balsara, Nitash P., Macromolecules 42, 4632 (2009)Google Scholar
44 Martinelli, Anne, Matic, Aleksandar, Jacobsson, Per, Borjesson, Lars, Fernicola, Alessandra and Scrosati, Bruno, J. Phys. Chem. 113, 11247 (2009)Google Scholar
45 Jang, Seung Soon, Molinero, Valeria, Cagin, Tahir, Goddard, William A. III , “Nanophase-Segregation and Transport in Nafion 117 from Molecular Dynamics Simulations: Effect of Monomeric Sequence”, Journal of Physical Chemistry B 108 3149 (2004)Google Scholar
46 Petersen, Matt K., Wang, Feng, Blake, Nick P., Metiu, Horia, and Voth, Gregory A. J. Phys. Chem. B109, 37273730 (2005)Google Scholar