4.8 Article

A high-performance hydroxide exchange membrane enabled by Cu2+-crosslinked chitosan

Journal

NATURE NANOTECHNOLOGY
Volume 17, Issue 6, Pages 629-+

Publisher

NATURE PORTFOLIO
DOI: 10.1038/s41565-022-01112-5

Keywords

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Funding

  1. University of Maryland A. James Clark School of Engineering and Maryland Nanocenter, its Surface Analysis Center
  2. AIMLab
  3. US National Institute of Standards and Technology [70NANB15H261]
  4. US Office of Naval Research [N00014-20-1-2186]
  5. US Department of Energy (DOE) Office of Science [DE-AC02-06CH11357]
  6. US DOE Office of Science Facilities at Brookhaven National Laboratory [DE-SC0012704]

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A Cu2+-crosslinked chitosan material is introduced as a stable and high-performance hydroxide exchange membrane, with excellent ion transport capacity and stability. The metal-crosslinking reaction forms nanochannels in chitosan, facilitating ion transport and achieving high power density in direct methanol fuel cells.
Ion exchange membranes are widely used to selectively transport ions in various electrochemical devices. Hydroxide exchange membranes (HEMs) are promising to couple with lower cost platinum-free electrocatalysts used in alkaline conditions, but are not stable enough in strong alkaline solutions. Herein, we present a Cu2+-crosslinked chitosan (chitosan-Cu) material as a stable and high-performance HEM. The Cu2+ ions are coordinated with the amino and hydroxyl groups of chitosan to crosslink the chitosan chains, forming hexagonal nanochannels (similar to 1nm in diameter) that can accommodate water diffusion and facilitate fast ion transport, with a high hydroxide conductivity of 67 ms cm(-1) at room temperature. The Cu2+ coordination also enhances the mechanical strength of the membrane, reduces its permeability and, most importantly, improves its stability in alkaline solution (only 5% conductivity loss at 80 degrees C after 1,000 h). These advantages make chitosan-Cu an outstanding HEM, which we demonstrate in a direct methanol fuel cell that exhibits a high power density of 305 mWcm(-2). The design principle of the chitosan-Cu HEM, in which ion transport channels are generated in the polymer through metal-crosslinking of polar functional groups, could inspire the synthesis of many ion exchange membranes for ion transport, ion sieving, ion filtration and more.

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