New combination of nanoparticles and graphene results in a more durable catalytic material for fuel cells

Mary Beckman, PNNL [Source]

Bracing catalyst in material makes fuel cell component work better and last longer

A nanoparticle of indium tin oxide (green and red) braces platinum nanoparticles (blue) on the surface of graphene (black honeycomb) to make a hardier, more chemically active fuel cell material. A new combination of nanoparticles and graphene results in a more durable catalytic material for fuel cells, according to work published today online at the Journal of the American Chemical Society. The catalytic material is not only hardier but more chemically active as well. The researchers are confident the results will help improve fuel cell design.

"Fuel cells are an important area of energy technology, but cost and durability are big challenges," said chemist Jun Liu. "The unique structure of this material provides much needed stability, good electrical conductivity and other desired properties."

Liu and his colleagues at the Department of Energy's Pacific Northwest National Laboratory, Princeton University in Princeton, N.J., and Washington State University in Pullman, Wash., combined graphene, a one-atom-thick honeycomb of carbon with handy electrical and structural properties, with metal oxide nanoparticles to stabilize a fuel cell catalyst and make it better available to do its job.

"This material has great potential to make fuel cells cheaper and last longer," said catalytic chemist Yong Wang, who has a joint appointment with PNNL and WSU. "The work may also provide lessons for improving the performance of other carbon-based catalysts for a broad range of industrial applications."

Muscle Metal Oxide

Fuel cells work by chemically breaking down oxygen and hydrogen gases to create an electrical current, producing water and heat in the process. The centerpiece of the fuel cell is the chemical catalyst — usually a metal such as platinum — sitting on a support that is often made of carbon. A good supporting material spreads the platinum evenly over its surface to maximize the surface area with which it can attack gas molecules. It is also electrically conductive.

Fuel cell developers most commonly use black carbon — think pencil lead — but platinum atoms tend to clump on such carbon. In addition, water can degrade the carbon away. Another support option is metal oxides — think rust — but what metal oxides make up for in stability and catalyst dispersion, they lose in conductivity and ease of synthesis. Other researchers have begun to explore metal oxides in conjunction with carbon materials to get the best of both worlds.

As a carbon support, Liu and his colleagues thought graphene intriguing. The honeycomb lattice of graphene is porous, electrically conductive and affords a lot of room for platinum atoms to work. First, the team crystallized nanoparticles of the metal oxide known as indium tin oxide — or ITO — directly onto specially treated graphene. Then they added platinum nanoparticles to the graphene-ITO and tested the materials.

Platinumweight

The team viewed the materials under high-resolution microscopes at EMSL, DOE's Environmental Molecular Sciences Laboratory on the PNNL campus. The images showed that without ITO, platinum atoms clumped up on the graphene surface. But with ITO, the platinum spread out nicely. Those images also showed catalytic platinum wedged between the nanoparticles and the graphene surface, with the nanoparticles partially sitting on the platinum like a paperweight.

To see how stable this arrangement was, the team performed theoretical calculations of molecular interactions between the graphene, platinum and ITO. This number-crunching on EMSL's Chinook supercomputer showed that the threesome was more stable than the metal oxide alone on graphene or the catalyst alone on graphene.

But stability makes no difference if the catalyst doesn't work. In tests for how well the materials break down oxygen as they would in a fuel cell, the triple-threat packed about 40% more of a wallop than the catalyst alone on graphene or the catalyst alone on other carbon-based supports such as activated carbon.

Last, the team tested how well the new material stands up to repeated usage by artificially aging it. After aging, the tripartite material proved to be three times as durable as the lone catalyst on graphene and twice as durable as on commonly used activated carbon. Corrosion tests revealed that the triple threat was more resistant than the other materials tested as well.

The team is now incorporating the platinum-ITO-graphene material into experimental fuel cells to determine how well it works under real world conditions and how long it lasts.

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Reference: Rong Kou, Yuyan Shao, Donghai Mei, Zimin Nie, Donghai Wang, Chongmin Wang, Vilayanur V Viswanathan, Sehkyu Park, Ilhan A. Aksay, Yuehe Lin, Yong Wang, Jun Liu, Stabilization of Electrocatalytic Metal Nanoparticles at Metal-Metal Oxide-Graphene Triple Junction Points, February 8, 2011, J. Am. Chem. Soc., DOI 10.1021/ja107719 (http://pubs.acs.org/doi/full/10.1021/ja107719u.

This work was supported by the U.S. Department of Energy Office of Energy Efficiency and Renewable Energy.

High-performance capacitor could lead to better rechargeable batteries

By Lisa Zyga @ physorg.com 

Abstract

Zeolite-templated carbon is a promising candidate as an electrode material for constructing an electric double layer capacitor with both high-power and high-energy densities, due to its three-dimensionally arrayed and mutually connected 1.2-nm nanopores. This carbon exhibits both very high gravimetric (140−190 F g⁻¹) and volumetric (75−83 F cm⁻³) capacitances in an organic electrolyte solution. Moreover, such a high capacitance can be well retained even at a very high current up to 20 A g⁻¹. This extraordinary high performance is attributed to the unique pore structure.

The unique 3D array of nanopores in zeolite-templated carbon enables it to be used as an electrode for high-performance supercapacitors that have a high capacitance and quick charge time. Image credit: Hiroyuki Itoi, et al. ©2011 American Chemical Society.

In order to develop next-generation electric vehicles, solar energy systems, and other clean energy technologies, researchers need an efficient way to store the energy. One of the key energy storage devices for these applications and others is a supercapacitor, also called an electric double-layer capacitor. In a recent study, scientists have investigated the possibility of using a material called zeolite-templated carbon for the electrode in this type of capacitor, and found that the material’s unique pore structure greatly improves the capacitor's overall performance.

To store energy, the electric double-layer capacitor is charged by ions that migrate from a bulk solution to an electrode, where they are adsorbed. Before reaching the electrode’s surface, the ions have to travel through narrow nanopores as quickly and efficiently as possible. Basically, the quicker the ions can travel down these paths, the quicker the capacitor can be charged, resulting in a high rate performance. Also, the greater the adsorbed ion density in the electrode, the greater the charge that the capacitor can store, resulting in a high volumetric capacitance.

Recently, scientists have been testing materials with pores of various sizes and structures to try to achieve both quick ion transport and high adsorption ion density. But the two requirements are somewhat contradictory, since ions can travel more quickly through larger nanopores, but large nanopores make the electrode density low and thus decrease the adsorbed ion density.

The zeolite-templated carbon consists of nanopores that are 1.2 nm in diameter (smaller than most electrode materials) and that have a very ordered structure (whereas other pores can be disordered and random). The nanopores’ small size makes the adsorbed ion density high, while the ordered structure – described as a diamond-like framework – allows the ions to quickly pass through the nanopores. In a previous study, the researchers showed that zeolite-templated carbon with nanopores smaller than 1.2 nm cannot enable fast ion transport, suggesting that this size may provide the optimal balance between high rate performance and high volumetric capacitance.

In tests, the zeolite-templated carbon’s properties exceeded those of other materials, demonstrating its potential to be used as an electrode for high-performance electric double-layer capacitors.

More information: Hiroyuki Itoi, et al. “Three-Dimensionally Arrayed and Mutually Connected 1.2-nm Nanopores for High-Performance Electric Double Layer Capacitor.” Journal of the American Chemical Society. DOI:10.1021/ja108315p