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New platinum-cobalt nanocatlysts for fuel cells greatly enhance activity and stability and cut costs

31 October 2012

A research team at the Energy Materials Center at Cornell (EMC2) is developing platinum-cobalt nanoparticles with a platinum enriched shell that show improved catalytic activity for the oxygen reduction reaction in fuel-cell applications. The new class of Pt–Co nanocatalysts—composed of ordered Pt3Co intermetallic cores with a 2–3 atomic-layer-thick platinum shell—exhibited a more than 200% increase in mass activity and a more than 300% increase in specific activity when compared with the disordered Pt3Co alloy nanoparticles as well as Pt/C.

The new material could reduce the cost by a factor of five, according to Héctor Abruña, the E.M. Chamot Professor of Chemistry and Chemical Biology, senior author of a paper describing the work published in the journal Nature Materials. The mass activity for the oxygen reduction reaction is the highest among the Pt–Co systems reported in the literature under similar testing conditions, the authors noted. These ordered nanoparticles provide a new direction for catalyst performance optimization for next-generation fuel cells, they suggested.

Stability tests showed a minimal loss of activity after 5,000 potential cycles and the ordered core–shell structure was maintained virtually intact, as established by atomic-scale elemental mapping. The researchers attributed the high activity and stability are attributed to the Pt-rich shell and the stable intermetallic Pt3Co core arrangement.

Previously, the Cornell research team created nanoparticles of a palladium-cobalt alloy coated with a thin layer of platinum that worked like pure platinum at lower cost. Forming the catalyst as nanoparticlesprovides more surface area to react with the fuel.

Deli Wang, a post-doctoral researcher in Abruña's group, devised a new chemical process to manufacture nanoparticles of a platinum-cobalt alloy that included an annealing step in which the randomly distributed atoms in the alloy form an orderly crystal structure. Platinum atoms layered onto these particles line up with the lattice and are pushed closer together than they would be in pure platinum, with the resulting strain enhancing the catalytic activity.

The Energy Materials Center at Cornell is an Energy Frontier Research Center funded by the US Department of Energy.

Resources

  • Deli Wang, Huolin L. Xin, Robert Hovden, Hongsen Wang, Yingchao Yu, David A. Muller, Francis J. DiSalvo & Héctor D. Abruña (2012) Structurally ordered intermetallic platinum–cobalt core–shell nanoparticles with enhanced activity and stability as oxygen reduction . Nature Materials doi: 10.1038/nmat3458

October 31, 2012 in Catalysts, Fuel Cells | Permalink | Comments (36) | TrackBack (0)

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Comments

Im interrested to buy more then ever. Im awaiting to buy a used hydrogen vehicle in 2022 approx.

I've got no idea what 5,000 cycles means in fuel cell terms.
It would be fantastic for a battery.

Huge fuel cell breakthroughs, like battery breakthroughs, are reported for decades.

Just sell something that can be publicly verified during another of the hydrogen initiative decades.

I wanted to ask, does anyone have any cost speculation on H2 fuelcell vehicles? Or more exactly, the cost of the fuelcell.


The more I read and understand about future battery chemistries the more and more I see H2 being the solution to the range anxiety.

Limitations to batteries' cycles, current,power densities, weight and volume could easily end a BEV. Yes, it will get cheeper and cheeper to impliment,but I feel that these two technologies will interesect, probably before the death of ICEs.

Heck I wouldn't mind it if we burned H2 instead of gasoline. 110 octane is always a plus. Even burning natural gas has tremendous benefits over good old 87. Not only in costs but it is an inherently cleaner fuel and there are no major technological breakthroughs keeping us from mass production/mass adoption.

The H2FC wants to be your primary energy supply, because it doesn't like voltage cycles (they corrode the catalyst) and the high capital cost.

This turns you from a captive consumer of the petroleum industry to a captive consumer of the natural gas industry (which is increasingly owned by petroleum majors like XOM).  Plug-in is the way to go; use liquid fuels to handle your range anxiety, just knock off the fuel consumption of the first 20-30 miles of every trip.

Hmm, a post of mine seems to have disappeared.

Here is a graph of the {non-existent) cycle degradation of this catalyst:
http://fuelcellsworks.com/news/2012/10/31/ordered-catalyst-boosts-fuel-cell-output-at-lower-cost/

That is about as flat a graph as I have seen as the cycles increase., and perhaps the answer to EP's point, although actually the cycle life of the cells used in the cars they are to produce by 2015 from a variety of manufacturers is already 'good enough'.

Here are the estimated costs on target by the DOE for fuel cells for transport:
'By 2017, a 60% peak-efficient, 5,000 hour durable, direct hydrogen fuel cell power system for transportation at a cost of $30/kW'

http://www.hydrogen.energy.gov/pdfs/review12/fc000_papageorgopoulos_2012_o.pdf

Although that is an aspiration, not an achievement, previous targets have been hit:

http://www.greencarcongress.com/2012/07/doefcv-20120718.html

There is essentially no reply to make to notions that hydrogen and fuel cells are all a plot by big oil, as that is a political attitude, not a technological critique, but it explains much of the opposition to fuel cells, and in my view often leads to unbalanced readings of the costs and potentials of the technology.

It seems to me that battery production, and the build of solar cells which many want to complete this supposed liberation from big business, are both the highest of high tech, and very big business indeed, so their use as a tool for liberation from the technological industrial complex is rather flawed.

What would be the energy hit to generate H2 at home from natural gas?

Life cycle efficiency -39.6%
External energy efficiency 60.4%
Net energy ratio 0.66

http://www.nrel.gov/docs/fy01osti/27637.pdf

page 14

It depends if you've got a use for the waste heat or not.  Small chemical systems are not very efficient, but if you'd be heating something anyway the losses matter a whole lot less.

The problem is that vehicle fuel is required year-round, and the waste heat would only be useful during the heating season (and even then there might be excess).

Actualy it MAINLY depends on what your costs for nat gas compared to others like kwh and liter of fuel are... in some places its such that converting nat gas to h2 and using a fuel cell saves a ton of money...

The hydrogen plant energy efficiency is 89.3%, on an HHV basis.

http://www.nrel.gov/docs/fy01osti/27637.pdf

Page 13

That is a large plant with steam reforming and gas shift, without compression. Honda Clarity has a home refueling station, but no data on that. I would say 70% for a home refueling station reforming natural gas, no gas shift and compression to 5000 psi. Just a guess. Propane and other unwanted substances in the pipeline have to be removed as well.

What are your kwh and gasoline prices and is your nat gas cheap or spendy? Realy its that simple.. I wouldnt think about a home reformer unless your sure you nat gas is gona stay cheap and your gasoline is gona stay above say 5 bucks a gal.

For home power... id say only concider it right now if your paying more then say 20 cents a kwh and even then be very careful to get rock solid numbers on cost per kwh your gona wind up paying so the gap is wide enough to pay for the dang systems.. they arnt cheap but prices are falling.

I have had far too many friends pay alot ofm money to .. future proof thier home.. with a long payout time.. and then have to move... OUCHIE.

A family of four uses a lot of hot water year round, so it would be good to reuse the heat of the conversion process.. You probably only need to make enough H2 for 40 miles of daily driving.

Thanks Dave,

So a 150Kw H2 fuelcell may just cost $4500??? and be overprovisioned enough(90Kw @ 60% efficiency) to drive most if not all passenger cars? Sure we may have to refill every 300miles due to range limitations. (I have a car with <13gal tank I think this will be more than enough for myself)

I know its not entirely efficient, but you can use electricity to generate H2 on site, and you could even use renewable sources.

and as others suggest, using existing natural gas infastructure to localize H2 genration even to the home, capturing heatlosses for other uses.

being a car guy, $4500 fuelcell compared to an engine that may cost OEMs $2000-8000+ is negligable. Though I probably suspect the $30/kW is extremely under valued. If it were that low, I'd hope to be driving a H2 car soon. It could almost be 3x as energy efficient as a conventional ICE, not to mention all that TQ.

The other side of the coin is that industrial-scale reformers can sequester CO2, and that's not going to happen with home-sized units.  Nobody's going to install a CO2 collection pipeline network running parallel to the NG distribution system, only backwards.

Looking at this from a different perspective, the H2FC car has a limited window of opportunity for adoption.  On the one side, batteries are rapidly going up in capacity and down in price; on the other side, work to convert biomass and waste to liquid fuels continues to make progress.  The H2FC car's niche is in the shrinking middle between these, and it's going to get too small to support the build-out of a hydrogen supply network sooner rather than later.

There is essentially no reply to make to notions that hydrogen and fuel cells are all a plot by big oil
It is not conspiracy that XOM has bought up natural gas companies, and sees its domestic future more in NG rather than conventional oil.  Neither is it a coincidence that one of the first actions by oilmen Bush and Cheney in 2001 was to replace PNGV with the hydrogen "Freedom Car".  There's no answer to these things because they're true, and the contrary position is false.

There's no reply to the claim that it's expensive and very inefficient to convert carbon-free power (solar, wind, nuclear) to hydrogen and back to electricity to run a car, whereas batteries return far more of the energy put into them.  It's true, period.  If you really do get 89.3% efficiency from CH4 to H2, it means that carbon fuels have the efficiency advantage for provision of H2, but not for electricity.  If your goal is to de-carbonize, hydrogen is not your friend.

There's also the detail that it takes barely 3% leakage of methane to make natural gas as much of a greenhouse threat as coal for the following century.  Given that most hydrogen would be made by steam-reforming of methane, this is not an issue that can be separated from H2FCVs.

@Folks,
Why worry about home production of H2, when the H2 will be available within short driving distance after 2015, and you can fill up a FCV in minutes, and can drive for another 300+ miles?

Reformation of NG can be done locally whereby the heat of reformation can be used for hot water heating and spa heating in the summer for hotels, hospitals, and apartment complexes, restaurants, and for living space heating of large buildings in the winter. The H2 filling stations will conveniently be located near major buildings where a lot of people will have quick access for a quick H2 refill, and the waste heat can be utilized. In tightly-knit housing complexes, insulated glycol-water pipes can also transport hot water among a serie of houses in order to utilize the waste heat of NG reformation or electrolysis.

Likewise, waste heat will be generated with the process of electrolysis of water, and can also be used similarly, in order to boost the energy efficiency of H2 production to near unity! Excess renewable-energy electricity will be absorbed by these electrolyzers and will raise the sale price of these moment of excess of RE electricity, or it will go to waste, or will command very low prices.

In more remote areas away from large buildings, H2 can also be made from electrolysis of water, and, since the waste heat can't be utilized there, the H2 will cost a little more, but will still be cheaper than petroleum when used in FCV having 50-60% efficiency, vs. ICEV with 15-20% typical efficiency.

H2 is the most efficient chemical fuel that can be synthesized from renewable energy, at current technology level.

@E-P,
>>>"Looking at this from a different perspective, the H2FC car has a limited window of opportunity for adoption. On the one side, batteries are rapidly going up in capacity and down in price; on the other side, work to convert biomass and waste to liquid fuels continues to make progress."

No matter how good batteries will get, H2FCV will have a secure place in the future. The H2 tank will last several times the life time of the car, without calendar life limitation like a battery. Now, FC stack have demonstrated remarkable durability as well. This will bode well for low cost of usage and high resale values. In colder climates, H2FCV can supply badly-needed waste heat for winter driving, and in hot climates, battery degradation will accelerate, and so, FCV will be more preferrable.

WRT biofuels, emission rules will be more and more tightened, such that by 2025, only FCV and NGV and BEV will be able to pass emission test. Petroleum-fueled car or liquid bio-fuel cars will have a hard time with later emission regulations unless equipped with expensive emission-control equipments, and may not be the vehicle of choice. Liquid bio-fuel may eventually cost $2.5/gallon retail per Cool Planet technology, but H2 will eventually cost that much or less, and FCV can go twice as far in comparison to an HEV, or 3-4 times as far in comparison to an equivalent ICEV for a given amount of fuel energy!

@E-P,
>>>"There's also the detail that it takes barely 3% leakage of methane to make natural gas as much of a greenhouse threat as coal for the following century. Given that most hydrogen would be made by steam-reforming of methane, this is not an issue that can be separated from H2FCVs."

Relax, E-P. We already have NG piping everywhere now, to a majority of homes, offices, buildings, etc. Whether NG will be used for H2 production or not, the NG leakage problem will NOT be worsen.

I would worry more about the use of NG in vehicles, because with every fillup, there will be a little bit of a leakage of NG into the atmosphere.

The H2 tank will last several times the life time of the car, without calendar life limitation like a battery.
In other words, either a market for reclaimed H2 tanks is needed or much of their value is scrapped with the vehicles.
WRT biofuels, emission rules will be more and more tightened, such that by 2025, only FCV and NGV and BEV will be able to pass emission test.
SOFCs and MCFCs will do; even ICEs with pre-heated catalysts will be in the running for a long time.  They can all burn liquid fuels.  I do not care for models assuming liquid biofuels and ICE-only prime movers because (a) biomass is insufficient and (b) drop-in replacements for petroleum maintains major markets for petroleum, but in a PHEV scenario petroleum is uncompetitive for the bulk of miles driven and eventually gets pushed out of the market.  Waste streams such as MSW need disposal regardless, and conversion to liquid fuels has the virtue of eliminating tipping fees.  We're bound to see something from that direction.

@SJC

Nice link to a LCA but you are completely wrong about the application. H2 is an important chemical feedstock for many processes. We will never use H2 as a fuel when it comes from CH4 because natural gas is a much better fuel and safer to handle.

“A family of four uses a lot of hot water year round ”

This is an old myth. With low flow shower nozzels and enzymes detergents, we do not use very much hot water. In any case, if NG is a very efficient way to make hot water.

The California hippies you to say that if you just conserve we will not have to build new nuke plants. That also applies to making electricity in your home. Once you do all the cost effective conservation measures, making your own power is just not cost effective.

LCA shows almost zero emissions for HTGCR for large volumes of H2 for chemical feedstock and LWR for making electricity.

We will never use H2 as a fuel when it comes from CH4 ...

Well if you are SO sure, I guess NO one will convince you. The fact that most of the H2 comes from CH4 now has no relevance.

The fact that H2 derived from CH4 costs far more than CH4 has great relevance.

Herm asked:

"What would be the energy hit to generate H2 at home from natural gas?"

I added information that might lead to an accurate conclusion, which is what I thought this forum was about.

It is not suppose to be about who can pretend they are right and insult everyone who does not agree.

No, you made a rhetorical statement.  You got another one in reply, dealing only with the same subject matter.  Taking personal offense at rhetorical replies to rhetoric is more than just a bit hypocritical.

It's true that most H2 is made by SMR.  One then needs to ask, what is it used for?  It's used for things like hydrodesulfurization, where there is no substitute; it is not used as process fuel because it is much more expensive than other fuels, including its own raw material.  Exceptions like forklifts have relatively small energy needs but high costs for downtime.

The model for H2FCVs is for the H2 to come from either electrolysis (very expensive) or chemical reforming of hydrocarbons.  The alleged object of carbon-free vehicles is only met if the carbon from the H2 production process is sequestered.  Can we guarantee this?  History is not a cause for optimism.  With nuclear power and BEV/PHEVs, we can be certain what the electric side will emit.

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