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Title: Engineered Transport in Microporous Materials and Membranes for Clean Energy Technologies

Authors:
 [1];  [2];  [3];  [1];  [4];  [5]; ORCiD logo [6]
  1. Department of Chemical and Biomolecular Engineering, The University of California, Berkeley CA 94720 USA
  2. Department of Chemistry, The University of California, Berkeley CA 94720 USA
  3. Department of Chemical Engineering, The Massachusetts Institute of Technology, Cambridge MA 02139 USA
  4. Materials Sciences Division, Lawrence Berkeley National Laboratory, 1 Cyclotron Rd Berkeley CA 94720 USA
  5. Department of Chemical and Biomolecular Engineering, The University of California, Berkeley CA 94720 USA, Department of Chemistry, The University of California, Berkeley CA 94720 USA, Materials Sciences Division, Lawrence Berkeley National Laboratory, 1 Cyclotron Rd Berkeley CA 94720 USA
  6. Materials Sciences Division, Lawrence Berkeley National Laboratory, 1 Cyclotron Rd Berkeley CA 94720 USA, The Molecular Foundry, Lawrence Berkeley National Laboratory, 1 Cyclotron Rd Berkeley CA 94720 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1416396
Grant/Contract Number:
SC0001015
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Advanced Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 8; Related Information: CHORUS Timestamp: 2018-02-22 10:04:47; Journal ID: ISSN 0935-9648
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Li, Changyi, Meckler, Stephen M., Smith, Zachary P., Bachman, Jonathan E., Maserati, Lorenzo, Long, Jeffrey R., and Helms, Brett A.. Engineered Transport in Microporous Materials and Membranes for Clean Energy Technologies. Germany: N. p., 2018. Web. doi:10.1002/adma.201704953.
Li, Changyi, Meckler, Stephen M., Smith, Zachary P., Bachman, Jonathan E., Maserati, Lorenzo, Long, Jeffrey R., & Helms, Brett A.. Engineered Transport in Microporous Materials and Membranes for Clean Energy Technologies. Germany. doi:10.1002/adma.201704953.
Li, Changyi, Meckler, Stephen M., Smith, Zachary P., Bachman, Jonathan E., Maserati, Lorenzo, Long, Jeffrey R., and Helms, Brett A.. Mon . "Engineered Transport in Microporous Materials and Membranes for Clean Energy Technologies". Germany. doi:10.1002/adma.201704953.
@article{osti_1416396,
title = {Engineered Transport in Microporous Materials and Membranes for Clean Energy Technologies},
author = {Li, Changyi and Meckler, Stephen M. and Smith, Zachary P. and Bachman, Jonathan E. and Maserati, Lorenzo and Long, Jeffrey R. and Helms, Brett A.},
abstractNote = {},
doi = {10.1002/adma.201704953},
journal = {Advanced Materials},
number = 8,
volume = 30,
place = {Germany},
year = {Mon Jan 08 00:00:00 EST 2018},
month = {Mon Jan 08 00:00:00 EST 2018}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on January 8, 2019
Publisher's Accepted Manuscript

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  • Selective ion transport across membranes is critical to the performance of many electrochemical energy storage devices. While design strategies enabling ion-selective transport are well-established, enhancements in membrane selectivity are made at the expense of ionic conductivity. To design membranes with both high selectivity and high ionic conductivity, there are cues to follow from biological systems, where regulated transport of ions across membranes is achieved by transmembrane proteins. The transport functions of these proteins are sensitive to their environment: physical or chemical perturbations to that environment are met with an adaptive response. Here we advance an analogous strategy for achieving adaptivemore » ion transport in microporous polymer membranes. Along the polymer backbone are placed redox-active switches that are activated in situ, at a prescribed electrochemical potential, by the device’s active materials when they enter the membrane’s pore. This transformation has little influence on the membrane’s ionic conductivity; however, the active-material blocking ability of the membrane is enhanced. We show that when used in lithium-sulfur batteries, these membranes offer markedly improved capacity, efficiency, and cycle-life by sequestering polysulfides in the cathode. Furthermore, the origins and implications of this behavior are explored in detail and point to new opportunities for responsive membranes in battery technology development« less
    Cited by 4
  • Selective ion transport across membranes is critical to the performance of many electrochemical energy storage devices. While design strategies enabling ion-selective transport are well-established, enhancements in membrane selectivity are made at the expense of ionic conductivity. To design membranes with both high selectivity and high ionic conductivity, there are cues to follow from biological systems, where regulated transport of ions across membranes is achieved by transmembrane proteins. The transport functions of these proteins are sensitive to their environment: physical or chemical perturbations to that environment are met with an adaptive response. Here we advance an analogous strategy for achieving adaptivemore » ion transport in microporous polymer membranes. Along the polymer backbone are placed redox-active switches that are activated in situ, at a prescribed electrochemical potential, by the device’s active materials when they enter the membrane’s pore. This transformation has little influence on the membrane’s ionic conductivity; however, the active-material blocking ability of the membrane is enhanced. We show that when used in lithium-sulfur batteries, these membranes offer markedly improved capacity, efficiency, and cycle-life by sequestering polysulfides in the cathode. Furthermore, the origins and implications of this behavior are explored in detail and point to new opportunities for responsive membranes in battery technology development« less
  • © 2017 American Chemical Society. Selective ion transport across membranes is critical to the performance of many electrochemical energy storage devices. While design strategies enabling ion-selective transport are well-established, enhancements in membrane selectivity are made at the expense of ionic conductivity. To design membranes with both high selectivity and high ionic conductivity, there are cues to follow from biological systems, where regulated transport of ions across membranes is achieved by transmembrane proteins. The transport functions of these proteins are sensitive to their environment: physical or chemical perturbations to that environment are met with an adaptive response. Here we advance anmore » analogous strategy for achieving adaptive ion transport in microporous polymer membranes. Along the polymer backbone are placed redox-active switches that are activated in situ, at a prescribed electrochemical potential, by the device's active materials when they enter the membrane's pore. This transformation has little influence on the membrane's ionic conductivity; however, the active-material blocking ability of the membrane is enhanced. We show that when used in lithium-sulfur batteries, these membranes offer markedly improved capacity, efficiency, and cycle-life by sequestering polysulfides in the cathode. The origins and implications of this behavior are explored in detail and point to new opportunities for responsive membranes in battery technology development.« less
  • This paper focuses on the preparation and characterization of pure TiO[sub 2] and ZrO[sub 2] xerogels. The preparation method is based on a sol-gel technique using metal tert-amyloxides as precursors to produce nano-sized metal oxide particles which are subsequently packed in a gelation process, eventually resulting in microporous xerogels. The unsupported TiO[sub 2]and ZrO[sub 2] xerogels produced in this manner have a mean pore diameter less than 2 nm and more than 50% microporosity. However, these gels, in their pure form, are thermally stable only to 350 C. Improved thermal stabilities of mixed metal oxide xerogels will be reported elsewhere.
  • The proposal of kinetic molecular sieving of hydrogen isotopes is explored by employing statistical rate theory methods to describe the kinetics of molecular hydrogen transport in model microporous carbon structures. A Lennard-Jones atom-atom interaction potential is utilized for the description of the interactions between H{sub 2}/D{sub 2} and the carbon framework, while the requisite partition functions describing the thermal flux of molecules through the transition state are calculated quantum mechanically in view of the low temperatures involved in the proposed kinetic molecular sieving application. Predicted kinetic isotope effects for initial passage from the gas phase into the first pore mouthmore » are consistent with expectations from previous modeling studies, namely, that at sufficiently low temperatures and for sufficiently narrow pore mouths D{sub 2} transport is dramatically favored over H{sub 2}. However, in contrast to expectations from previous modeling, the absence of any potential barrier along the minimum energy pathway from the gas phase into the first pore mouth yields a negative temperature dependence in the predicted absolute rate coefficients - implying a negative activation energy. In pursuit of the effective activation barrier, we find that the minimum potential in the cavity is significantly higher than in the pore mouth for nanotube-shaped models, throwing into question the common assumption that passage through the pore mouths should be the rate-determining step. Our results suggest a new mechanism that, depending on the size and shape of the cavity, the thermal activation barrier may lie in the cavity rather than at the pore mouth. As a consequence, design strategies for achieving quantum-mediated kinetic molecular sieving of H{sub 2}/D{sub 2} in a microporous membrane will need, at the very least, to take careful account of cavity shape and size in addition to pore-mouth size in order to ensure that the selective step, namely passage through the pore mouth, is also the rate determining step.« less