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Title: Editors' Choice—Connecting Fuel Cell Catalyst Nanostructure and Accessibility Using Quantitative Cryo-STEM Tomography

Abstract

Further reduction of Pt in hydrogen fuel cells is hampered by reactant transport losses near the catalyst surface, especially for degraded catalysts. Strategically mitigating these performance losses requires an improved understanding of the catalyst nanostructure, which controls local transport and catalyst durability. We apply cryo-tomography in a scanning transmission electron microscope (STEM) to quantify the three-dimensional structure of carbon-supported Pt catalysts and correlate to their electrochemical accessibility. We present results for two carbon supports: Vulcan, a compact support with a large majority of Pt observed on the exterior, and HSC, a porous support with a majority of Pt observed within interior carbon pores, which have relatively constrictive openings. Increasing Pt content shifts the Pt distribution to the exterior on both carbon supports. By correlating to the electrochemical surface area, we find that all Pt surface area is accessible to protons in liquid. However, the interior Pt fraction quantitatively tracks Pt utilization losses at low humidity, indicating that the interior Pt is inaccessible to the proton-conducting ionomer, likely because narrow carbon pore openings block ionomer infiltration. These results imply different proton transport mechanisms for interior and exterior Pt, and quantitatively describe the catalyst structure, supporting development of transport and durability models.

Authors:
ORCiD logo [1];  [1];  [2]; ORCiD logo [3];  [3];  [4];  [1];  [3];  [3];  [3];  [5]
  1. Cornell Univ., Ithaca, NY (United States)
  2. General Motors Co., Warren, MI (United States)
  3. General Motors Co., Pontiac, MI (United States)
  4. Honda R&D Co. Ltd., Haga, Tochigi (Japan)
  5. Cornell Univ., Ithaca, NY (United States); Kavli Inst. at Cornell for Nanoscale Science, Ithaca, NY (United States)
Publication Date:
Research Org.:
General Motors Co., Warren, MI (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Fuel Cell Technologies Office (EE-3F)
OSTI Identifier:
1423148
Alternate Identifier(s):
OSTI ID: 1509886
Grant/Contract Number:  
EE0007271
Resource Type:
Published Article
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 165; Journal Issue: 3; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Carbon support; Nanostructure; Transport

Citation Formats

Padgett, Elliot, Andrejevic, Nina, Liu, Zhongyi, Kongkanand, Anusorn, Gu, Wenbin, Moriyama, Koji, Jiang, Yi, Kumaraguru, Swami, Moylan, Thomas E., Kukreja, Ratandeep, and Muller, David A. Editors' Choice—Connecting Fuel Cell Catalyst Nanostructure and Accessibility Using Quantitative Cryo-STEM Tomography. United States: N. p., 2018. Web. doi:10.1149/2.0541803jes.
Padgett, Elliot, Andrejevic, Nina, Liu, Zhongyi, Kongkanand, Anusorn, Gu, Wenbin, Moriyama, Koji, Jiang, Yi, Kumaraguru, Swami, Moylan, Thomas E., Kukreja, Ratandeep, & Muller, David A. Editors' Choice—Connecting Fuel Cell Catalyst Nanostructure and Accessibility Using Quantitative Cryo-STEM Tomography. United States. doi:10.1149/2.0541803jes.
Padgett, Elliot, Andrejevic, Nina, Liu, Zhongyi, Kongkanand, Anusorn, Gu, Wenbin, Moriyama, Koji, Jiang, Yi, Kumaraguru, Swami, Moylan, Thomas E., Kukreja, Ratandeep, and Muller, David A. Tue . "Editors' Choice—Connecting Fuel Cell Catalyst Nanostructure and Accessibility Using Quantitative Cryo-STEM Tomography". United States. doi:10.1149/2.0541803jes.
@article{osti_1423148,
title = {Editors' Choice—Connecting Fuel Cell Catalyst Nanostructure and Accessibility Using Quantitative Cryo-STEM Tomography},
author = {Padgett, Elliot and Andrejevic, Nina and Liu, Zhongyi and Kongkanand, Anusorn and Gu, Wenbin and Moriyama, Koji and Jiang, Yi and Kumaraguru, Swami and Moylan, Thomas E. and Kukreja, Ratandeep and Muller, David A.},
abstractNote = {Further reduction of Pt in hydrogen fuel cells is hampered by reactant transport losses near the catalyst surface, especially for degraded catalysts. Strategically mitigating these performance losses requires an improved understanding of the catalyst nanostructure, which controls local transport and catalyst durability. We apply cryo-tomography in a scanning transmission electron microscope (STEM) to quantify the three-dimensional structure of carbon-supported Pt catalysts and correlate to their electrochemical accessibility. We present results for two carbon supports: Vulcan, a compact support with a large majority of Pt observed on the exterior, and HSC, a porous support with a majority of Pt observed within interior carbon pores, which have relatively constrictive openings. Increasing Pt content shifts the Pt distribution to the exterior on both carbon supports. By correlating to the electrochemical surface area, we find that all Pt surface area is accessible to protons in liquid. However, the interior Pt fraction quantitatively tracks Pt utilization losses at low humidity, indicating that the interior Pt is inaccessible to the proton-conducting ionomer, likely because narrow carbon pore openings block ionomer infiltration. These results imply different proton transport mechanisms for interior and exterior Pt, and quantitatively describe the catalyst structure, supporting development of transport and durability models.},
doi = {10.1149/2.0541803jes},
journal = {Journal of the Electrochemical Society},
number = 3,
volume = 165,
place = {United States},
year = {2018},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1149/2.0541803jes

Citation Metrics:
Cited by: 7 works
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Web of Science

Figures / Tables:

Figure 1 Figure 1: Illustration of electron tomography procedure, shown for 50wt%Pt/Vulcan catalyst nanoparticles. High signal to noise ratio (SNR), distortion-free images are produced by summing aligned stacks of fast-acquisition STEM images. A tilt series of images, acquired as the specimen tilts from approximately −75° to 75° at 2° intervals, is alignedmore » to a common coordinate system and reconstructed to a 3D image of the specimen. The reconstruction is segmented to identify the material type represented in each voxel to allow quantitative analysis and more informative visualization, for instance here showing the carbon surface in gray, interior Pt particles in blue, and exterior Pt particles in red.« less

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.