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DOE reports progress on development of low-carbon and renewable sources of hydrogen production

The US Department of Energy (DOE) Fuel Cell Technologies Office’ (FCTO) 2014 Hydrogen and Fuel Cells Program Annual Progress Report (earlier post)—an annual summary of results from projects funded by DOE’s Hydrogen and Fuel Cells Program—described progress in the field of hydrogen production.

The objective of the Hydrogen Production sub-program is to reduce the cost of hydrogen dispensed at the pump to a cost that is competitive on a cents-per-mile basis with competing vehicle technologies. Based on current analysis, this translates to a hydrogen threshold cost of <$4 per kg hydrogen (produced, delivered, and dispensed, but untaxed) by 2020, apportioned to <$2/kg for production only.

H2prod
Range of hydrogen production costs, untaxed, for near- to mid-term distributed and centralized pathways. The high end of each bar represents a pathway-specific high feedstock cost as well as an escalation of capital cost; while the low end reflects a low end on feedstock costs and no capital escalation. Bars for different years in the same pathway represent improvements in the costs of the specific pathway, based on specific reference data for the appropriate year and pathway. Source: DOE. Click to enlarge.

For FY 2014, the Hydrogen Production sub-program continued to focus on developing technologies to enable the long-term viability of hydrogen as an energy carrier for a range of applications with a focus on hydrogen from low-carbon and renewable sources. Progress continued in several key areas, including electrolysis, photoelectrochemical (PEC), biological, and solar-thermochemical hydrogen production.

There are multiple DOE offices are engaged in R&D relevant to hydrogen production. FCTO’s focus is developing technologies for distributed and centralized renewable production of hydrogen. Distributed production options under development include reforming of bio-derived renewable liquids and electrolysis of water. Centralized renewable production options include water electrolysis integrated with renewable power generation (e.g., wind, solar, hydroelectric, and geothermal power), biomass gasification, solar-driven high- temperature thermochemical water splitting, direct photoelectrochemical water splitting, and biological processes.

In addition:

  • The Office of Fossil Energy (FE) is advancing the technologies needed to produce hydrogen from coal-derived synthesis gas, including co-production of hydrogen and electricity. Separate from the Hydrogen and Fuel Cells Program, FE is also developing technologies for carbon capture, utilization, and storage, which could eventually enable hydrogen production from coal to be a near-zero-emissions pathway.

  • The Office of Science’s Basic Energy Sciences (BES) program conducts research to expand the fundamental understanding of biological and biomimetic hydrogen production, photoelectrochemical water splitting, catalysis, and membranes for gas separation.

  • The Office of Nuclear Energy (NE) is currently collaborating with EERE on a study of nuclear-renewable hybrid energy systems. Many of the systems being evaluated by this study use hydrogen production as a form of energy storage or as an input to industrial processes. The previous major hydrogen activity in NE, the Nuclear Hydrogen Initiative, was discontinued in Fiscal Year (FY) 2009 after steam electrolysis was chosen as the hydrogen production pathway most compatible with the next generation nuclear power.

In FY 2014, the major emphasis of the electrolysis activities were cost reduction and efficiency improvement through leveraging fuel cell catalyst development. Among the developments here were:

  • A nano-structured thin film catalyst anode technology was tested under electrolysis conditions and demonstrated comparable performance at 1/16th of the anode PGM loading relative to a 2013 baseline.

  • The manufacture of core shell catalyst technology developed by Brookhaven National Laboratory was successfully transferred to its facility and achieved equivalent cathode performance at 1/10th of the cathode PGM loading relative to the 2013 baseline.

  • An improved drying technique was developed with the potential to reduce drying losses in electrolyzers to less than 3.5% (compared with 11-8% in commercial systems) while operating on a variable (wind or solar) stack power profile. Testing is in progress to verify that the new technique meets SAE International Standard J2719 specifications for water content (<5 ppm).

In the area of photoelectrochemical (PEC) hydrogen production, semiconductor tandem devices were shown to have more than 300 hours of stability at ~15 mA/cm2 in III-V semiconductor photoelectrochemical tandem devices, showing a significant improvement over the previous year’s 115 hours at 10 mA/cm2. This result represents an important step toward demonstration of stabilized solar-to-hydrogen conversion efficiencies >20% using PEC devices.

In the area of biological hydrogen production, a larger, more scalable microbial reverse-electrodialysis cell design demonstrated a 0.9 L/L-reactor/day hydrogen production rate, a 12.5% increase over the 2013 demonstrated rate, using a salinity gradient instead of grid electricity. Other technical progress in this area included:

  • Increased activity of the Chlamydomonas strain was demonstrated expressing the Ca1 hydrogenase from 2% to about 11% of the native hydrogenase, with a duration of 30 minutes or more.

  • The genome of the bacterium Rubrivivax gelatinosus Casa Bonita Strain (CBS) was examined for candidate genes to transfer to the cyanobacteria Synechocystis to improve the expression and activity of the non-native CBS hydrogenase enzyme. The researchers identified slyD, involved in binding and inserting Ni into the hydrogenase active site, as a likely gene as it is present in CBS but absent in Synechocystis. Researchers also improved the Synechocystis expression of the CBS maturation protein HypF, which is involved in assembling the active hydrogenase enzyme, up to nine-fold.

  • The truncated light-harvesting antenna concept was applied to cyanobacteria, demonstrating that a Δcpc strain of Synechocystis, which is missing the phycobilisome portion of the photosynthetic antenna, can reach higher light levels before saturation than the wild type and has 55-60% greater rates of biomass accumulation.

Efforts in solar-thermochemical hydrogen characterized the performance of water splitting by novel, non-volatile metal-oxide based reaction materials and developed new reactor concepts to optimize efficiency of the reaction cycles. Other progress included:

  • Over three times improvement in hydrogen production was demonstrated relative to 2013 results of 100 micromole/g for isothermal operation at 1,350 ˚C for hercynite cycle materials using near-isothermal reduction/oxidation cycling.

  • Integration of major components into a pressurized button cell test facility was completed for the electrolysis step of the Hybrid Sulfur thermochemical cycle that will allow testing of catalysts and membranes at pressures up to 1 MPa and temperatures of 130oC. The team identified and screened electrocatalysts with the potential to reduce oxidation overpotential by >20 mV versus the state-of-the-art platinum catalyst. Savannah River National Laboratory (SRNL) also tested thin-film electrodes as candidate anode electrocatalysts, including Pt, Pd, Ir, Au, PtAu, and PtV. Au, PtAu and PtV showed 28 mV, 46 mV, and 13 mV reduction, respectively, on the anode polarization versus state-of-the-art Pt catalyst.

Pathway-specific milestones planned for FY 2015 in the Hydrogen Production sub-program projects include:

  • Demonstrate fermentation of deacetylated corn stover lignocellulose in a sequencing fed-batch bioreactor and obtain a hydrogen production rate of 450 mL H2/L/d with a total hydrogen output of 80% of that of avicel cellulose based on the same amount of cellulose loading (5 g/L).

  • Deliver 100 feet of roll-to-roll produced electrolysis catalyst with a durability of <20 mV drop after 1,000 hours of operation at 1.5 A/cm2, and with a total PGM loading of less than 0.5 mg/cm2.

  • Demonstrate the viability of stabilized photoelectrochemical systems with >15% solar-to-hydrogen efficiency using advanced tandem devices based on either III-V crystalline semiconductor or chalcopyrite thin-film semiconductor materials.

  • Develop a monolith reactor concept for integration of steam reforming reactions with in situ carbon dioxide capture and heat transfer for high-throughput hydrogen production from bio-oils. Identify optimum reforming catalysts and sorbents for >80% of equilibrium hydrogen yield at T <500°C, and >90% carbon dioxide capture under reaction conditions.

  • Continue development of conceptual designs for fully integrated solar thermochemical prototype reactors and synthesis and evaluation of perovskite and hercynite reaction materials. Demonstrate the production of spray-dried active materials that produce at least 150 μmol H2/g total and reduction of at least 1 gram of oxidized spray-dried active materials under vacuum pumping to remove released O2, and oxidation of at least 1 gram reduced spray- dried active materials with steam to produce hydrogen.

  • Completion of H2A v3 case studies for bio-fermentation and high-temperature solid oxide electrolysis hydrogen production pathways.

Comments

Bob Wallace

You're having to create unusual situations in order to claim a higher efficiency. There needs to be a demand for the heat when the hydrogen is compressed and a need for the heat when the fuel cell is operated. Possible, but kind of hard to imagine factories that would snuggle up to the H2 operations and switch back and forth to the hydrogen plant as they needed heat.

And your home use. Someone is going to pay a bundle for a hydrogen plant in order to heat their bathtub?

Germany is looking at hydrogen because it can store some without compression. That avoids a lot of the energy loss.

Japan, who knows. It feels like someone in the Japanese government is a H2 true believer and hasn't made an objective analysis. We've got the two big Japanese auto manufacturers backing FCEVs which, based on Toyota's cost analysis, are deemed to fail. You can't win in a market if you off a product that costs 3x to 6x as much to operate as the competition.

I don't know, Roger. I've read what I can find that explains how hydrogen fits into our long term energy needs but all I can see is the possibility for a bit as deep backup. And even then it looks like there are likely better options.

Here's what I see you doing, Roger. You start with a belief that hydrogen is the answer. And then you try to build arguments to support your belief. That's pretty much a "religious" approach. Why not try to list out the facts and let the facts drive your opinion? That way it's easier to shift ones opinion as new facts emerge. If you approach the issue as a believer then you are likely going to be forced to deny inconvenient facts and mislead yourself.

(Just to be clear. In terms of hydrogen energy storage I don't have a formed opinion. I see a possibility for a minor role but I don't know enough to move things past "maybe" at this point. Based on what I know about H2 FCEVs my opinion is that they are not likely to succeed. If data appears that shows them to have some distinct advantage over EVs then my opinion will shift.)

Roger Pham

@Bob,
Hydrogen will simply replace Natural Gas and Coal. Very simple.
If our economy depends on NG and Coal today, it will depend on hydrogen tomorrow.

Hydrogen offers many advantages over NG and Coal.
EFFICIENCY:
FUEL CELL is twice as efficient as small combustion engines without the difficult to remove exhaust emission. It is quiet and emission free so can be placed in residential area.
WASTE HEAT UTILIZATION: This can double the efficiency of central power plant, even for CCGT.
RELIABILITY: Power lines are very vulnerable to storms and solar flares. Having your own FC generator is both practical and a status symbol.
TOTALLY OFFGRID IN SUNNY AREAS: Huge rooftop solar storing excess power in battery for evening use while sending excess power as hydrogen into local hydrogen piping for winter and rainy day use can go totally off grid. The grid is an expensive thing costing you 3-5 cent per kWh extra for distribution cost, yet unreliable. Why not make your own power and your own transportation fuel and your winter heating fuel all on Hydrogen?
HYDROGEN IS NOT A GHG, unlike NG, which has 20x the GHG index of CO2. NG will need to be phased out just on the basis of its GHG problem alone.

Sorry, Bob, your exclusion of H2 was implicitly based on dependency on NG and coal for power backup and winter heating. A macrogrid will be a very expensive thing and vulnerable infrastructure, yet still dependent on NG power generation backup and for home and office heating. In winters, RE's output will be insufficient to provide for heating needs without depending on NG or coal. Hydrogen allows us to overcome dependency on fossil fuels altogether.

HarveyD

The lowest cost solution is rarely the best solution.

H2 may currently cost more than Coal, Oil or NG but it is much cleaner and often more efficient.

To survive, we may have to start using the cleanest solution instead of the cheapest.

In the long term, we may not have the choice because we will run out of Coal, Oil and NG.

Bob Wallace

Hello, Mr. Roger! Hello!

Please list the car companies now selling EVs and PHEVs. And then list for us the car companies selling FCEVs.

If you find your second list a bit slim, feel free to add the two? companies that have announced that they definitely will have FCEVs for sale within the next two years.

In order to make H2 less lossy you go through a lot of twists and turns to find a use for the waste heat. That would not be as cheap and easy as you think. H2 extraction and compression plants would have to snuggle up to factories needing heat. And that would increase distribution costs. Cars simply don't need much heat. For much of the year any fuel cell heat is going to be totally discarded.

Roger Pham

@Harvey,
Thank you for the voice of reason.

@Bob,
What you see as difficulties, I see as opportunities. Eventually, the Nat Gas in our pipings will need to be replaced with H2. With cheap frack NG here is USA, it will take longer here than for countries that have to import NG, like Europe and Asia.

So, the H2 piping system will connect H2 producers and consumers, except that the H2 producers can be distributed due to the high efficiencies of smaller-scale electrolyzers.
Plus, since solar PV power will be distributed, placing electrolyzers nearby solar PV fields will negate transmission cost, distribution cost, and the cost and loss of efficiency in converting DC to AC then DC again!

So, here's the picture:
The huge parking lots and roof areas of food processing plants, hotels, spas, hospitals, malls, schools, universities, business districts, factories...etc will be covered with solar PV panels, to directly serving the consumers nearby, thereby bypassing the grid almost entirely, except perhaps for small power lines for wind electricity! Talking about vast savings in cost of grid infrastructure and maintenance!
Where else would you locate the electrolyzers and the Fuel cells, Mr. Bob? Then, the routing of cooling loop of anti-freeze /water to and from the electrolyzers and Fuel cells to the water heater or boiler would be a piece of cake, and opportunistic.

So, electrolyzers would be located close to where day-time heat would be needed, while fuel cells would be located where evening-time heat would be needed. With a large-enough water reservoir, some time-shifting would still be practical.
Thus, a future 100%-reliable-DC microgrid with inverters used only for legacy AC equipments. Future motorized appliances can use DC brushless motors with the motor controllers designed to operate on a wide range of DC voltages. DC to DC converters can be used for LED lighting and electronics, capable of wide range of DC voltages. No more ugly overhead power lines!!!

You see, when heat is needed, H2's efficiency can approach 100%, no matter whether waste heat or just heat from a burner. When the waste heat of electrolysis is also used, the round-trip efficiency can approach 100% without any major effort.

What about H2 compression? The electrolyzers deliver the H2 already compressed enough for release into the H2 pipings (50-500psi), at near isothermal compression for maximal efficiency, so there would be no waste heat available! Small foil-bearing turbines can be used to recover these compression energy before feeding into the fuel cells to recuperate most of energy used in compression.

H2 compression at the FCEV filling stations (10,000psi) are of liquid-piston-type using ionic liquid to compress the H2 at near isothermal for maximal efficiency and no waste heat available!

WRT waste heat of FCEV's, FCEV's produce 1/2 to 1/3 the waste heat of ICEV's! This is a major improvement in energy efficiency. Most of FCEV's waste heat is warm enough and is useful for winter use.
BEV's have poor efficiency in winters, and sadly, the waste heat of BEV's are of too low temperatures in winter to be useful.

HarveyD

FCEVs, PHEVs and BEVs may become more complementary than many posters think.

They are bascially e-vehicles with a few variants.

1. BEVs are the most basic clean vehicles but require larger, heavier more costly batteries for extended range and are rather slow to recharge. Range is limited if used in very cold climate.

2. PHEVs and FCEVs are modified BEVs with smaller battery pack but with ICE or FC range extenders. Total range can be extended with larger fuel tanks. Re-fuelling (with H2 or liquid fuels) is very quick but much more costly than for BEVs. Can operate in cold climate areas and waste heat can be used to keep passengers at comfortable level.

Currently, PHEVs with ICE range extender are cheaper to operate than FCEVs but produce more GHGs and pollution.

In the not too distant future, H2 will be much cheaper and could match liquid fuels cost. When that happens, PHEVs (and ICEVs) will be progressively phased out.

BEVs and FCEVs may co-exist for a long time and as long as batteries have not sufficently evolved to become more compeitive, specially for extended range and larger vehicles.

Bob Wallace

I agree with your overall position to some extent, but I wonder where we find the route to cheaper hydrogen? Even at Toyota's "best future" price of 10 cents a mile it's still more expensive than gasoline.

Assuming that we don't put a price on carbon which would change the math -

PHEVs use, on average, fuel for about 15% of miles driven. That would make for a small market for H2. Possibly not enough for economies of scale to push prices from 17c to 10c per mile.

It wouldn't be a large enough market for a H2 filling station on every corner but might support some along highways where people need the extra range. Filling convenience would be low compared to gasoline. We'll have a lot of gas station for more than a decade after the last ICEV is sold.

If someone goes into their dealer's showroom and is faced with a choice of a gas PHEV with <7c/fueled mile and a H2 PHEV with <10c/fueled mile why would they pick the H2 model?

Roger Pham

@Bob,
>>>>"If someone goes into their dealer's showroom and is faced with a choice of a gas PHEV with <7c/fueled mile and a H2 PHEV with <10c/fueled mile why would they pick the H2 model?"

Good point, Bob. There are 2 reasons I can think of for now :
1) More ZEV credit for the H2-PHEV, perhaps will induce the OEM's to lower its price.
2) Perhaps gasoline availability will be much reduced in the future, while H2 will be ubiquitous. Petroleum or synthetic fuels must be transported thousands of miles to refinery, then distributed thousands of miles away from the refinery. The H2 can be produced in-situ.

Bob Wallace

" Petroleum or synthetic fuels must be transported thousands of miles to refinery, then distributed thousands of miles away from the refinery. The H2 can be produced in-situ."

That's correct, Roger. But there's a couple of problems.

1) You're assuming someone puts up the money to build H2 infrastructure. You know the problems of finding that sort of money for a shaky investment.

2) The petroleum industry is going to linger for more than a decade after the last ICEV is sold.

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