Tag Archives: metal-air batteries

Spinach could help power fuel cells.

Leave a reply
By Source (WP:NFCC#4), Fair use, https://en.wikipedia.org/w/index.php?curid=65303730

I was surprised to see a reference to the cartoon character, Popeye, in the headline (although it’s not carried forward into the text) for this October 5, 2020 news item on ScienceDaily about research into making fuel cells more efficient,

Spinach: Good for Popeye and the planet

“Eat your spinach,” is a common refrain from many people’s childhoods. Spinach, the hearty, green vegetable chock full of nutrients, doesn’t just provide energy in humans. It also has potential to help power fuel cells, according to a new paper by researchers in AU’s Department of Chemistry. Spinach, when converted from its leafy, edible form into carbon nanosheets, acts as a catalyst for an oxygen reduction reaction in fuel cells and metal-air batteries.

…

An October 5, 2020 American University news release (also on EurekAlert) by Rebecca Basu, which originated the news item, provides more detail about the research,

An oxygen reduction reaction is one of two reactions in fuel cells and metal-air batteries and is usually the slower one that limits the energy output of these devices. Researchers have long known that certain carbon materials can catalyze the reaction. But those carbon-based catalysts don’t always perform as good or better than the traditional platinum-based catalysts. The AU researchers wanted to find an inexpensive and less toxic preparation method for an efficient catalyst by using readily available natural resources. They tackled this challenge by using spinach.

“This work suggests that sustainable catalysts can be made for an oxygen reduction reaction from natural resources,” said Prof. Shouzhong Zou, chemistry professor at AU and the paper’s lead author. “The method we tested can produce highly active, carbon-based catalysts from spinach, which is a renewable biomass. In fact, we believe it outperforms commercial platinum catalysts in both activity and stability. The catalysts are potentially applicable in hydrogen fuel cells and metal-air batteries.” Zou’s former post-doctoral students Xiaojun Liu and Wenyue Li and undergraduate student Casey Culhane are the paper’s co-authors.

Catalysts accelerate an oxygen reduction reaction to produce sufficient current and create energy. Among the practical applications for the research are fuel cells and metal-air batteries, which power electric vehicles and types of military gear. Researchers are making progress in the lab and in prototypes with catalysts derived from plants or plant products such as cattail grass or rice. Zou’s work is the first demonstration using spinach as a material for preparing oxygen reduction reaction-catalysts. Spinach is a good candidate for this work because it survives in low temperatures, is abundant and easy to grow, and is rich in iron and nitrogen that are essential for this type of catalyst.

Zou and his students created and tested the catalysts, which are spinach-derived carbon nanosheets. Carbon nanosheets are like a piece of paper with the thickness on a nanometer scale, a thousand times thinner than a piece of human hair. To create the nanosheets, the researchers put the spinach through a multi-step process that included both low- and high-tech methods, including washing, juicing and freeze-drying the spinach, manually grinding it into a fine powder with a mortar and pestle, and “doping” the resulting carbon nanosheet with extra nitrogen to improve its performance. The measurements showed that the spinach-derived catalysts performed better than platinum-based catalysts that can be expensive and lose their potency over time.

The next step for the researchers is to put the catalysts from the lab simulation into prototype devices, such as hydrogen fuel cells, to see how they perform and to develop catalysts from other plants. Zou would like to also improve sustainability by reducing the energy consumption needed for the process.

Here’s a link to and a citation for the paper,

Spinach-Derived Porous Carbon Nanosheets as High-Performance Catalysts for Oxygen Reduction Reaction by Xiaojun Liu, Casey Culhane, Wenyue Li, and Shouzhong Zou. ACS Omega 2020, 5, 38, 24367–24378 DOI: https://doi.org/10.1021/acsomega.0c02673 Publication Date:September 15, 2020 Copyright © 2020 American Chemical Society

This paper appears to be open access.

Get the platinum out

1 Reply

They’ve been using platinum catalysts, in fuel cells and metal-air batteries, which over the last five years has ranged in cost from just under $800/oz to over $2200/oz. My March 13, 2012 posting about fuel cells noted that the use of expensive metals that are not very efficient catalysts was holding back their development and entry into the marketplace,

Advances in fuel-cell technology have been stymied by the inadequacy of metals studied as catalysts. The drawback to platinum, other than cost, is that it absorbs carbon monoxide in reactions involving fuel cells powered by organic materials like formic acid. A more recently tested metal, palladium, breaks down over time.

Now chemists at Brown University have created a triple-headed metallic nanoparticle that they say outperforms and outlasts all others at the anode end in formic-acid fuel-cell reactions.

Another group of researchers at Stanford University and other institutions is suggesting an alternative to a platinum catalyst, a multi-walled carbon nanotube. From the May 27, 2012 news release written by Mark Shwartz on EurekAlert,

Multi-walled carbon nanotubes riddled with defects and impurities on the outside could replace some of the expensive platinum catalysts used in fuel cells and metal-air batteries, according to scientists at Stanford University. Their findings are published in the May 27 online edition of the journal Nature Nanotechnology.

“Platinum is very expensive and thus impractical for large-scale commercialization,” said Hongjie Dai, a professor of chemistry at Stanford and co-author of the study. “Developing a low-cost alternative has been a major research goal for several decades.”

…

For the study, the Stanford team used multi-walled carbon nanotubes consisting of two or three concentric tubes nested together. The scientists showed that shredding the outer wall, while leaving the inner walls intact, enhances catalytic activity in nanotubes, yet does not interfere with their ability to conduct electricity.

“A typical carbon nanotube has few defects,” said Yanguang Li, a postdoctoral fellow at Stanford and lead author of the study. “But defects are actually important to promote the formation of catalytic sites and to render the nanotube very active for catalytic reactions.”

Here’s how it works, from the May 27, 2012 news release on EurekAlert,

For the study, Li and his co-workers treated multi-walled nanotubes in a chemical solution. Microscopic analysis revealed that the treatment caused the outer nanotube to partially unzip and form nanosized graphene pieces that clung to the inner nanotube, which remained mostly intact.

“We found that adding a few iron and nitrogen impurities made the outer wall very active for catalytic reactions,” Dai said. “But the inside maintained its integrity, providing a path for electrons to move around. You want the outside to be very active, but you still want to have good electrical conductivity. If you used a single-wall carbon nanotube you wouldn’t have this advantage, because the damage on the wall would degrade the electrical property.”

These are two different perspectives on the reason for why fuel cells and other batteries have not had the expected impact on the marketplace. The team at Brown University states the problem as an issue with the effectiveness of the metal catalysts where the Stanford-led team states the problem as being the cost of the metal used. Dexter Johnson in a March 9, 2012 posting on the Nanoclast blog on the IEEE (Institute of Electrical and Electronics Engineers) website suggested a third issue,

One of the fundamental problems with fuel cells has been the cost of producing hydrogen. While hydrogen is, of course, the most abundant element, it attaches itself to other elements like nitrogen or fluorine, and perhaps most ubiquitously to oxygen to create the water molecule. The process used to separate hydrogen out into hydrogen gas for powering fuel cells now relies on electricity produced from fossil fuels, negating some of the potential environmental benefits.

In his May 30, 2012 posting about this new work from Stanford, Dexter notes yet another issue impeding widespread commercialization,

… but the two main issues that have prevented fuel cells from gaining wider adoption—at least in the area of powering automobiles—are the costs of isolating hydrogen and building an infrastructure that would deliver that hydrogen to the automobiles.

Dexter mentions another application (metal-air batteries) that may benefit more from this latest work (from Dexter’s May 30, 2012 posting),

I think it’s all together possible that researchers at IBM and the US national labs who have been working on metal-air batteries for years now might be somewhat more interested in this line of research than fuel-cell manufacturers.

As one of the researchers notes (from the May 27, 2012 news release on EurekAlert),

“Lithium-air batteries are exciting because of their ultra-high theoretical energy density, which is more than 10 times higher than today’s best lithium ion technology,” Dai said. “But one of the stumbling blocks to development has been the lack of a high-performance, low-cost catalyst. Carbon nanotubes could be an excellent alternative to the platinum, palladium and other precious-metal catalysts now in use.”

The Stanford team made one other discovery as they were testing the carbon nanotubes,

The Stanford study might also have resolved a long-standing scientific controversy about the chemical structure of catalytic active sites where oxygen reactions occur. “One group of scientists believes that iron impurities are bonded to nitrogen at the active site,” Li said. “Another group believes that iron contributes virtually nothing, except to promote active sites made entirely of nitrogen.”

To address the controversy, the Stanford team enlisted scientists at Oak Ridge National Laboratory to conduct atomic-scale imaging and spectroscopy analysis of the nanotubes. The results showed clear, visual evidence of iron and nitrogen atoms in close proximity.

“For the first time, we were able to image individual atoms on this kind of catalyst,” Dai said. “All of the images showed iron and nitrogen close together, suggesting that the two elements are bonded. This kind of imaging is possible, because the graphene pieces are just one-atom thick.”

Dai noted that the iron impurities, which enhanced catalytic activity, actually came from metal seeds that were used to make the nanotubes and were not intentionally added by the scientists. The discovery of these accidental yet invaluable bits of iron offered the researchers an important lesson. “We learned that metal impurities in nanotubes must not be ignored,” Dai said.