Sunday, August 21, 2005

 

Current status of hydrogen storage

Posted by ben @ 9:55 PM | Permanent Link

Hydrogen storage is the biggest technical challenge that we have to overcome if we want to be driving hydrogen fueled cars. The problem with hydrogen is that it’s the smallest molecule in the world, with 2 protons and 2 electrons, and so it’s very difficult to store. You can’t pump hydrogen through a natural gas pipeline for instance because it will diffuse through the steel and you’ll end up losing most of your hydrogen before you can use it. You have to be very careful what materials you use to store hydrogen too because, just say you’re storing it as a gas, the hydrogen molecules in the gas cylinder are continuously moving around and hitting the sides of the cylinder and so it actually structurally weakens the gas cylinder. So there’s a lot challenges in storing hydrogen. There are a couple of ways of doing it though. Of course there’s the compressed hydrogen gas storage or you can liquefy hydrogen and store it as a liquid, or you can store hydrogen in carbon nanotubes or you can store it in a solid like sodium borohydride for example, which has a chemical formula of NaNH4, and when you react NaBH4 with a base, you end up with hydrogen gas and some other things.


Here's a podcast about the current status of hydrogen storage.

As explained in the podcast, the Department of Energy is focusing on compressed hydrogen (5000-10000psi) and liquefied hydrogen for near term hydrogen fueled vehicles. The long term plan is to develop solid state hydrogen storage, which means metal hydrides and chemical hydrides. The overall goal is to allow vehicles to travel for 300 miles without refueling.

More specifically, by 2010, the DOE wants to develop and verify on-board hydrogen storage systems achieving 2 kWh/kg (6 wt%), 1.5 kWh/L, and $4/kWh.; by 2015, 3 kWh/kg (9 wt%), 2.7 kWh/L, and $2/kWh.

Here's a quick overview of some of the hydrogen storage technologies that the D.O.E. is working on:


Compressed Hydrogen

The simplest way of storing hydrogen is to compress hydrogen and stuff it into a gas cylinder at very high pressures. Right now we can store hydrogen gas pretty easily at a pressure of 5000psi. And obviously the higher the pressure, the more hydrogen you can store. But at 5000psi, we don’t meet that 300 mile range that the D.O.E is targeting, and so the solution is to use higher pressures. Right now there’s work going towards 10000psi compressed hydrogen gas tanks, which is progressing very nicely and will get us up to the 300 mile range, and it’ll reach the 6 wt% hydrogen requirement, but there are extra costs associated with the materials that are needed to get up to those pressures and the fabrication methods don’t seem to be very flexible so meeting the cost target is the big issue. Another problem with compressed hydrogen is that it’s very expensive to fill up. Compressing hydrogen to 10000psi is not cheap, energy wise, for anybody interested, going from atmospheric pressure, which is 14.5psi to around 10000psi requires 2.21kWh/kg of H2, that’s the equivalent of 10 cents Canadian per kg of hydrogen, for me at least, which would add about 50 cents to the cost of a fill up because 5kg of hydrogen will do you about 300 miles these days. An extra 50 cents doesn’t sound that bad, but it would be about 25% of the cost of filling up with hydrogen, which is targeted to cost $1.5/kg.


A lot of people are also concerned of having compressed gas cylinders in their cars though, because they think that if they get into an accident, then having 5000psi or 10000psi gas cylinders would be just like having a rocket in their car, if the gas cylinder ruptures, then there is trouble. I think it’s probably a valid fear, the gas tanks are pretty strong in some locations but at the neck they can be very weak, I’ve heard stories of these gas cylinders going through huge concrete walls and actually there’s a scene from the last James Bond movie where he’s chasing somebody in a hospital in Cuba and blows a hole through the wall with a gas cylinder, that’s what it would be like in your car. But on the other hand, hydrogen leaking through the gas cylinder isn’t really a problem.


Current cost status:
5000psi tanks: $15/kWh (73% reduction in costs)
10000psi tanks: $18/kWh (78% reduction in costs)


Liquid Hydrogen

Hydrogen can be stored as a liquid in a cryogenic container. But first you have to cool it down to -240C, which is -400deg F, which is 33 Kelvin. That’s cold. This has two problems, first of all the amount of energy required to liquefy the hydrogen, and also what’s known as the boil-off effect. The energy required to cool hydrogen from room temperature to -240C is somewhere between 1/3rd to 1/2 of the energy content per unit weight of hydrogen. So that means that if you’re going to be liquefying hydrogen, you’ll only be able to use half of the potential energy of hydrogen, which doesn’t start you off on the right foot. The idea of liquefying hydrogen is pretty much dead. To make things worse, at those low temperatures, hydrogen will boil off, even if the cryogenic container has the best insulation, hydrogen will boil off and the gas will leak out of the container. So it’s not an option for anybody except NASA.


Current status:
$6/kWh (33% reduction in costs)


Solid State Systems: Metal Hydrides and Chemical Hydrides

Ok, this type of hydrogen storage can get pretty complicated and I’m not up to speed on it, I know there’s at least one listener out there who used to work on metal hydrides, maybe he could explain it to us. So from what I gather, there are metal hydrides and complex hydrides, and I think the complex hydrides are sometimes also called chemical hydrides. Basically what happens for metal hydrides is that the metals will absorb hydrogen, and in the process of absorbing hydrogen, lots of heat is released. If you want to get that hydrogen back, then you have to supply heat and the hydrogen will be released for you to use in your car. So you would have some type of metal chunk in your car supplying hydrogen when it’s needed. The big challenge here is to find the right combination of metals that will release hydrogen by supplying the minimum amount of heat. For example, MgH2 requires 25% more energy to release the hydrogen than what’s contained in the hydrogen, so we can’t use that. Then there’s a group called the complex metal hydrides, which are looking more promising. The reason why they’re better involves a lot of chemistry which I don’t want to learn about or talk about, but one promising complex metal hydride is lithium boro-hydride, or LiBH4, which can hold about 18% hydrogen by weight. So remember the goal by 2010 is to hold 6% hydrogen by weight, but that’s 6% by weight of the entire system and this 18% is only by weight of the complex metal hydride, it doesn’t include any balance of plant components that might be needed. But nevertheless, it sounds promising. Another promising material is NaBH4, my friend Flora Lo does research on NaBH4, what happens is you react it with a base and you get hydrogen and some other stuff that has sodium and boron in it. The big problem is getting the right rate of hydrogen and that depends on how fast the NaBH4 reacts with the base. So, as far as I know, NaBH4 is one of the most promising long hydrogen storage methods in the long term because it can be recycled and it can hold lots of hydrogen.


Technical challenges:
There are lots, mostly because these systems are still very much in the research and development stage. They include hydrogen capacity, right now they just can’t store enough, the regeneration of these hydrides and also the lifetime of these hydrides isn’t very long right now, you can’t go through many cycles. Also, people just don’t understand how they work, there aren’t any test protocols or independent testing facilities, and it’s still a little tricky to envision how these hydrides would work exactly, how would you refill your chemical or metal hydride, it would have to be a lot different concept than going up to a gas station and filling up with hydrogen, it might involve taking the spent hydride out, physically, and trading it in for a hydride full of hydrogen.


Metal Hydrides Current status:
$16/kWh (75% reduction in costs)
Chemical Hydrides Current status:
$16/kWh (50% reduction in costs)


Figure 1 and Figure 2 below show the improvements over today's technology that is required for each of the hydrogen storage techniques to meet the 2010 and 2015 targets respectively.

Figure 1 and Figure 2 below show the improvements over today's technology that is required for each of the hydrogen storage techniques to meet the 2010 and 2015 targets respectively.




Figure 1. Improvement over today's technology that is required to meet DOE hydrogen storage targets by 2010.





Figure 2. Improvement over today's technology that is required to meet DOE hydrogen storage targets by 2015.



Liquefied hydrogen looks good in these two figures but the problem is the energy associated with cooling the hydrogen to -240C (-400F), which is between 1/3rd - 1/2 of the hydrogen's higher heating value (142 MJ/kg). The cost/kWh doesn't include the cost of cooling the hydrogen, just the cost of the materials.


Figure 3 and 4 show the current status of hydrogen storage technologies in absolute terms.





Figure 3. The current status of today's hydrogen storage technologies in voulmetric and gravimetric terms.





Figure 4. The cost of today's hydrogen storage technologies.



Hydrogen storage is definitely a big concern. But all of these targets that have been set by the DOE are to make hydrogen fuel competitive with gasoline so that the end user will have a minimal behavioral change. What if our behavior now is wrong though?



Comments:
The an ideal refridgerator requires 12.02 MJ/kg to liquefy H2. The process is complicated somewhat by the conversion from ortho to para-hydrogen. Realistically, if the figure of merit for Claude or Heylandt systems is around 0.3 now, they might be able to push it up to 0.4, which would be 20 % of the fuel's energy content.

Hydride storage problems are amusingly similar to battery issues.
 
I do not agree with the case of MgH2.
We produce in Europe special MgH2 + catalyst to be used with thermal engines and we could use the heat of exhaust of the engine for H2 release.
see Hystory project in EC
 
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