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Berkeley Lab team develops new high-performance solid-state H2 storage material: graphene oxide (GO)/Mg nanocrystal hybrid

12 March 2016

Researchers at Lawrence Berkeley National Laboratory (Berkeley Lab) have developed a new, environmentally stable solid-state hydrogen storage material constructed of Mg nanocrystals encapsulated by atomically thin and gas-selective reduced graphene oxide (rGO) sheets.

This material, protected from oxygen and moisture by the rGO layers, exhibits dense hydrogen storage (6.5 wt% and 0.105 kg H2 per liter in the total composite). As rGO is atomically thin, this approach minimizes inactive mass in the composite, while also providing a kinetic enhancement to hydrogen sorption performance.

These multilaminates of rGO-Mg are able to deliver exceptionally dense hydrogen storage and provide a material platform for harnessing the attributes of sensitive nanomaterials in demanding environments. An open-access paper on the work is published in the journal Nature Communications.

Hydrogen is the ultimate carbon-free energy carrier—it possesses the highest energy density among chemical fuels and water is the sole combustion product. Although major car manufacturers have made commitments to hydrogen as a ‘fuel of the future’, hydrogen storage for FCEVs (fuel cell electric vehicles) currently relies on compressed gas tanks. These are unable to meet long-term storage targets and severely compromise on-board occupancy.

Metal hydrides for solid-state hydrogen storage are one of the few materials capable of providing sufficient storage density required to meet these long-term targets. However, simultaneously meeting gravimetric, volumetric, thermodynamic and kinetic requirements has proven challenging, owing to the strong binding enthalpies for the metal hydride bonds, long diffusion path lengths and oxidative instability of zero-valent metals. Although nanostructuring has been shown to optimize binding enthalpies3, synthesis and oxidative stabilization of metallic nanocrystals remains a challenge. Protection strategies against oxidization and sintering of nanocrystals often involve embedding these crystals in dense matrices, which add considerable ‘dead’ mass to the composite, in turn decreasing gravimetric and volumetric density. Thus, although metal hydrides show the most promise for non-cryogenic applications, it remains true that no single material has met all of these essential criteria.

Here we demonstrate mixed dimensional reduced graphene oxide (GO)/Mg nanocrystal hybrids as a novel high-performance materials platform for solid-state hydrogen storage.

—Cho et al.

These graphene-encapsulated magnesium crystals act as “sponges” for hydrogen, offering a very compact and safe way to take in and store hydrogen. The nanocrystals also permit faster fueling, and reduce the overall “tank” size.

The graphene shields the nanocrystals from oxygen and moisture and contaminants, while tiny, natural holes allow the smaller hydrogen molecules to pass through. This filtering process overcomes common problems degrading the performance of metal hydrides for hydrogen storage.

Graphene-sheets-magnesium-nanocrystal
Thin sheets of graphene oxide (red sheets) have natural, atomic-scale defects that allow hydrogen gas molecules to pass through while blocking larger molecules such as oxygen (O2) and water (H2O). Berkeley Lab researchers encapsulated nanoscale magnesium crystals (yellow) with graphene oxide sheets to produce a new formula for metal hydride fuel cells. (Jeong Yun Kim) Click to enlarge.

Among metal hydride-based materials for hydrogen storage for fuel-cell vehicle applications, our materials have good performance in terms of capacity, reversibility, kinetics and stability.

—Eun Seon Cho, postdoc at Berkeley Lab and lead author

The research, conducted at Berkeley Lab’s Molecular Foundry and Advanced Light Source, is part of a National Lab Consortium, dubbed HyMARC (Hydrogen Materials—Advanced Research Consortium) (earlier post) that seeks safer and more cost-effective hydrogen storage.

Co-author Jeff Urban, a Berkeley Lab staff scientist, is Berkeley Lab’s lead scientist for HyMARC.

This work suggests the possibility of practical hydrogen storage and use in the future. I believe that these materials represent a generally applicable approach to stabilizing reactive materials while still harnessing their unique activity—concepts that could have wide-ranging applications for batteries, catalysis, and energetic materials.

—Jeff Urban

The work was supported by the Department of Energy Office of Basic Energy Sciences and Office of Energy Efficiency and Renewable Energy, the Bay Area Photovoltaic Consortium (BAPVC), and the US-India Partnership to Advance Clean Energy-Research (PACE-R) for the Solar Energy Research Institute for India and the US (SERIIUS).

Resources

  • Eun Seon Cho, Anne M. Ruminski, Shaul Aloni, Yi-Sheng Liu, Jinghua Guo & Jeffrey J. Urban (2016) “Graphene oxide/metal nanocrystal multilaminates as the atomic limit for safe and selective hydrogen storage” Nature Communications 7, Article number: 10804 doi: 10.1038/ncomms10804

March 12, 2016 in Graphene, Hydrogen, Hydrogen Storage | Permalink | Comments (20)

Comments

It seems that H2 storage diversity could soon overtake EV batteries diversity? Will that be good or bad for future FCEVs growth?

Of course, improved room temperature solid state, low pressure, compact H2 storage could be a key factor for lower cost extended range FCEVs together with lower cost FC home power emergency units.

Anti-FCEVs posters may have to review their objection, specially those living in cold weather areas.

This would allow lower pressures to store the same amount. One hundred pounds could store three kilograms of hydrogen, enough to go 150 miles.

More hydrogen pipe dreams. They did not mention this super advanced hydrogen storage system cost 30k USD per car and need replacement after 150k miles. Then add cost for fuel cells that cost another 10k USD and cleric motors and power electronics that cost another 10k USD for a low power 130kw system. Not to mention that there is not enough platinum on this planet for mass production of fuel cell cars and that hydrogen cost 3 times as much to drive one mile as the most efficient gassers and 6 times as much as a typical battery electric car.

Hydrogen car will always be more expensive to buy than gassers and battery electric vehicles. Moreover, they will always be much more costly to fuel than gassers and battery electric so they really are a pipedream. Only imbeciles and con-artists are advocating them.

Battery electric cars cost more than gassers to buy but cost far less than gassers to fuel. So the trick for battery electric cars to become more economic than gassers is to put as many miles on the battery electric car as possible in order to save more money on low fuel cost. You do that by making a self-driving Uber style taxi service where each taxi is doing 100k miles per year with customers paying 20 cents per mile. It starts in 2020. Those automakers that do not produce such robo-taxies in 2020 or shortly thereafter will all bankrupt. By 2030 there will not be a market left for gassers in any market segment and the market for ownership of sub 50k USD cars will not exist apart from a used-old-gassers market with heavily discounted prices.

@Henrik:

If you assume that the costs of graphene based materials will never drop, you can come out with whatever cost figures you fancy.

This storage method comes out to around 2kwh/kg, after allowing for conversion losses back to electricity the equivalent of around a 1kwh/kg battery.

And we can already hit that kind of energy density using the rather less attractive in some respects cylinder storage.

That is equivalent to one heck of a battery.

But of course you are assuming all sorts of improvements in the technologies you fancy, and none at all in those you don't.

I can't see FCs ever gaining a foothold in the broad market. Momentarily a FC, at a size needed for mobility purposes, costs ca. 75,000.00 USD. Let the price drop (wishful thinking) to 10% of that amount due to mass production scale and you'll end up by 7,500.00 USD for the FC only. Far too expensive!
The FKLG, invented from DLR in Germany, is a linear multi-fuel capable combustion engine. This engine is simple, small, light, and extremely reliable and efficient ; also runs on H2. The price for a single unit at mass production amounts to max. 2,000.00€. I'd definitely prefer that to an overly expensive and complicated FC.
http://www.dlr.de/dlr/en/desktopdefault.aspx/tabid-10084/161_read-8869/year-all/

An automated plant should be able to produce future various size FCs (without precious metals) very cheaply.

Coupled with adequate size SS H2 storage, the combo would fit in all size of AWD and AW FC vehicles and as home emergency power units. The plug-in SS H2 storage units would fit both the family FCEVs and Home fixed units. Alternatively, one the family FCEVs could be used as the home emergency power unit for 1+ week without refill.

It is too soon to write-off FCs (fixed and mobile) and FCEVs.

Harvey, your vision that ''happy motoring' is the quintessential of human happiness is comic to say the least....even cars powered electrically or by H2 it won't solve the problem of congestion in big cities, and people be obese by spending too much time in their cars and other undesirable side effects of this counter productive car centric culture. If you dream of a perfectly clean oil free mean of transportation, take your bike, you will do a great thing for your health and for the quality of life in cities. Industrial automated plans cranking fuel cells by the millions is nothing romantic you know

Davemart, Harvey et al.

There are of course the various ancillaries to the storage including the tank which is not as awkward as LH2 but likely heavier than many other energy storage sytems as well as the recovery system plumbing and control etc that should be added to the KWH/KG number.

To put all this in perspective I would ask you to read carefully from the respected author. I say respected as they certainly deserve respect for speaking plainly and honestly without gilding the lily or beating their drum.

They say there are serious obstacles to overcome.

We are only discussing the on board storage problems there is a whole other level of difficulty concerning efficient production storage and distribution.

There are also ** ethical political considerations regarding the ownership and control of energy supply.****

If I buy a rechargeable battery at any scalable dimension, I can fill it up at my leisure from any electron generator. - An exercise bike or my domestic solar, wind, hydro, grid, etc and do work.


I can recharge at any location electrons are available.

This is not only very convenient it is sensible.

I own the rechargeable battery and the cost is from dollars to tens of thousands.

It also happens to be very economical from my perspective and very efficient from an energy conservation perspective.

From the above I can see middle men (resellers) losing out.

The resellers may be business or gov'ts.
Gov'ts obviously need cash flow to fund common services.

Business need a plan that is attractive to it's customer.

It would seem (to many) the amount of disregard for the environmental damage from fossil fuels and the reluctance to raise funds from the people and business that live of the work of ordinary persons as well as the global nationalist indifference to political controling behaviour that facilitates mass human suffering, we need to be more concious, aware and critical in our thinking and recognise but not accept or assist those elements.

from the above article:


" Hydrogen is the ultimate carbon-free energy carrier—it possesses the highest energy density among chemical fuels and water is the sole combustion product. Although major car manufacturers have made commitments to hydrogen as a ‘fuel of the future’, hydrogen storage for FCEVs (fuel cell electric vehicles) currently relies on compressed gas tanks. These are unable to meet long-term storage targets and severely compromise on-board occupancy.

Metal hydrides for solid-state hydrogen storage are one of the few materials capable of providing sufficient storage density required to meet these long-term targets. However, simultaneously meeting gravimetric, volumetric, thermodynamic and kinetic requirements has proven challenging, owing to the strong binding enthalpies for the metal hydride bonds, long diffusion path lengths and oxidative instability of zero-valent metals. Although nanostructuring has been shown to optimize binding enthalpies3, synthesis and oxidative stabilization of metallic nanocrystals remains a challenge. Protection strategies against oxidization and sintering of nanocrystals often involve embedding these crystals in dense matrices, which add considerable ‘dead’ mass to the composite, in turn decreasing gravimetric and volumetric density. Thus, although metal hydrides show the most promise for non-cryogenic applications, it remains true that no single material has met all of these essential criteria."

Here we demonstrate mixed dimensional reduced graphene oxide (GO)/Mg nanocrystal hybrids as a novel high-performance materials platform for solid-state hydrogen storage."

"This work" **** "suggests the possibility of practical hydrogen storage and use in the future." **** "I believe that these materials represent a generally applicable approach to stabilizing reactive materials while still harnessing their unique activity—concepts that could have wide-ranging applications for batteries, catalysis, and energetic materials."

I don't suggest H2 has any qualities other than as a 'virtuous element '
I just don't see it holds a candle to the currently available system.
That does not mean that it cannot be the best solution from the perspective of (say) Industrial scale requirement. - I can't speak for those but - it would seem to have acceptable efficiency for large industrial scale capture of surplus electrons and capable of releasing at high intensity.

Grid storage makes sense. Industrial sites with the necessary proper qualified personnel and operational safety standards would seem appropriate.

With the current state of H2 technology.

Would it be appropriate or just foolish to site adjacent to museums, hospitals , the White house Kremlin Duma or the palace? The local shopping district?

That would inspire confidence.

600 pounds of fuel cell and tanks could go 300 miles and refill in 5 minutes. 600 pounds of batteries might to 100 miles and take half an hour to recharge.

200 mile Chevy Bolt battery is 960 lbs, that would make ~100 miles range less than 480 lbs.

EVs have the added advantage of starting every day with full fuel. Charge time is irrelevant when it happens while the driver is sleeping. To the EV driver, "refueling time" is only the time it takes to plug and unplug. For the FCV driver, any fair evaluation of refueling time would include driving time to and from the H2 station. For the next several years at least, those are not in every neighborhood, so drive time will not be insignificant.

Refuel time is almost irrelevant when considering the higher costs of the fuel station. $4,000,000 for a hydrogen station vs $400,000 for an EV charging station with equivalent capacity (cars refueled per day). At some point, the customer is going to have to foot the bill.

We have yet to see what the Bolt range really is. We know what the LEAF range is and it decreases over time.

Let's not forget that 50+% of potential electrified vehicle users do not have access to overnight charging facilities and will have to use public chargers for 30+ minutes about every day.

FCEVs with their inherent extended range (500 to 800 Km) will only need one ultra quick (3 minutes) refill per week, much the same as for existing ICEVs.

Low pressure SS H2 tanks will become a way to store H2 for extended periods for longer trips and for home fixed units much the same way as people handle their BBQ gas tanks. Refills/exchange will become easy and cheap.

FCEVs with high capacity H2 tank will become ideal emergency e-power generators for extended periods (1+ week) at almost no extra cost.

Downtown and highway congestion can be solved different ways with:

1) more subways
2) more e-buses
3) more suburban e-trains with multi-level large garages at each stop.
4. automated drive shared e-cars/e-minibus.

People would only drive to the nearest e-train or subway station with their e-car or shared e-vehicle.

Fuel Cells may definitely have a future and metal hydride hydrogen storage could be part of that solution. Check out the Toshiba H2One System, a Hydrogen Based Energy Supply System that is now providing electricity all year long to a Kyushu Resort Hotel (http://toshiba-ttda.com/2016/03/14/toshiba-h2one-hydrogen-based-autonomous-energy-supply-system-now-providing-power-to-a-kyushu-resort-hotel/). It also uses a metal hydride H2 storage tank (possibly based on technology similar to the Ovonics Hydride storage that used a magnesium alloy, which would definitely relate to this Berkeley Lab research). The system uses solar, batteries, H2 electrolysis/fuel cells. Since it is combined heat and power it probably has efficiency of 95%.
Key system specifications:
Photovoltaic capacity: 62 kW
Fuel cell output: 54kW
Electricity storage capacity: 1.8MWh
Hot water supply capacity: 24 liters maximum per minute.

Recent progress in SS H2 storage, Solar cells cost and efficiency and FCs makes solar energy more interesting and competitive.

Ontario, Canada is closing a very large 4,000 mega-watt CPP facility in favour of solar and wind REs.

The production cost per kWh will be higher but the huge reduction in GHG and pollution will offset most of it. The Green Fund from progressive Carbon fees/taxes could be used to offset most of the initial extra cost.

HD> 50+% of potential electrified vehicle users do not have access to overnight charging facilities and will have to use public chargers for 30+ minutes about every day.

That is easily solved by installing parking lot and street parking for overnight charging. These cars are parked somewhere while their owners sleep. If a city can install streetlights and parking meters, they can install charging. Wireless charging even eliminated the cord. It would cost less than 1/10 the cost of hydrogen infrastructure, and 1/10 the ongoing fuel costs.

Workplace charging is another easier and cheaper solution. Solar canopies provide power and protection from the elements. Businesses and colleges are already installing them in California.

200 mile batteries, like the Bolt will have, mean most commuters could charge as infrequently as once or twice a week. Twice a week would allow up to ~20,000 miles per year travel.

Agree with you that 250,000,000+ slow, wired and/or wireless charging spots could be installed in USA but very few cities will willingly assume the high associated price. Street wireless charging spots could cost well over $10K each and many times more where aerial or underground cables have to be added/changed.

Assuming an average of $10K each, the total cost could be in order of $2500B to $5000B.

On the other hand, a good clean national H2 station network could be built for about the same cost an even for a lot less with future technologies.

The economics of Hfcv have already droped 10 fold since GM started the equinox fuel cell project. Toyota est cost was over 100k for the fuel cell but now they have reduced that cost to less then 50K. The ablity to print these fuel cells is coming rapidly. The 7 kg hydrogen tank is less then 10k for 700 BAR , so if the berkely crew can get some angel funding across the bay, the miracle of Silicon valley can advance the tech 10 fold at 1/10 th price if there is more then 1,000,000 buyers. We are half way there with lithium in tesla 400,000 electric cars on the road. The main difference from the S model would be 1/2 the weight and possibly the fc 1/2 cost of 200 kWh battery given the 10 year head start by batteries. Everyday there is a new advance in fuelcell materials reducing platinum now to less then is in the catalytic converters. Lithium tech twill never be able to reduce the raw material by a factor of 10 like fuel cells have all ready done. Its just a matter of the VC 's getting the new tech through the valley of death to critical mass sales.

Oboma first energy secretary seriously delayed the research on fuel cells in favor of batteries but by end of his tenure , the funding flipped and now is much more focused on hydrogen. Obama sees that no matter how many incentives battery cars are just not that popular still less then 1%. in fad friendly Southern California Hydrogen FCV will grow rapidly with free fueling at hyndai and toyota. Japan is skipping the lithium battery incentives going straight to FC. Batteries will not beable to maintain moore law like fuel cells.

Hope that SOLARSURFER is correct and that affordable (various size) FCEVs and a thin basic clean (with high efficiency electrolisers using Hydro electricity) H2 Station network will be available in about 5 years in our cold weather area.

Our family would trade-in 2 of 3 of our Toyota HEVs, probably the Camrys Hybrid?

Researchers at the University of Toronto have found a much cheaper and much more efficient way to split water into H2 and O2.

Once fine-tuned and mass produced, their electrolizer could store electricity from REs as H2 for extended periods. Coupled with SS H2 storage tanks, it could become the back-bone of future low cost clean H2 stations for FCEVs and H2 for fixed e-power units.

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