Hydrogen Technologies and Applications
Resources, Processes & Materials Engineering
LECTURE 12b
Distinguished Professor Discipline of Physics and Astronomy
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School of EECMS
Faculty of Science and Engineering
Curtin University, WA, Australia
Lecture focus
Reproduced from “Materials and Man’s Needs”, National Academy of Sciences, Washington D.C., 1974.
Acknowledgements
A/Prof. , Dr Drew Sheppard, Dr Terry Humphries, Dr Veronica Sofianos, Dr Kasper Moller, Dr Yu Liu, Dr Mauricio Di Lorenzo, Dr Adriana , Dr Jacob Javadian, , , Mariana Tortoza, , ,
ARC Grants LP120100435, LP150100730, DP150101708, LP190100297, DP200102301 ARC LIEF Grants LE0775551, LE0989180, LE120100026, LE140100075, LE170100199 TEXEL, ITP Thermal, WA Hydrogen, Ausnational Investments Pty Ltd
Global Innovation Linkage Grant – Dept. of Industry, Science, Energy and Resources Future Energy Exports (FEnEx) Cooperative Research Centre (CRC) and Science.
Lecture Outline
Solar Power and Hydrogen
Why Hydrogen?
Hydrogen Storage Research Group (HSRG) Projects Conclusion
The Power of the Sun
• The World’s current power consumption is 18.3 TW
• The incident solar power on the planet is 166 PW
• 30% of this is reflected back into space, and 19% is absorbed by clouds
• This leaves a balance of 85 PW available for terrestrial solar collectors
• 85 PW is well over 4500 times our current world consumption of 18.3 TW
Solar Power
other Renewable Sources
. Of the IEEE 98 (2010) 42 – 66.
• All other sources of renewable energy are less than 1% of solar.
• If we consider the solar power that hits the desert regions of the world, all other renewables still only amount to less than 3% of this power.
Solar Power as the Dominant Renewable Source
If we globally tap sunlight over only 1% of the incident area at only an energy conversion efficiency of 1%, this meets our current world energy consumption of 18.3 TW.
As 9% of the planet surface area is taken up by desert and efficiencies well over 1% are possible, in practice, this opens up many exciting future opportunities.
Specifically, we find solar thermal collection via parabolic reflectors where focussed sunlight heats steam to about 600° C to drive a turbine is the best available technology for generating electricity.
What is the solar thermal collector footprint?
Worst case scenario 1300 km × 1300 km. With less pessimistic assumptions only 500 km × 500 km (approx. 1% of the land area of the Worlds hot deserts) would be required.
. Of the IEEE 98 (2010) 42 – 66.
Fossil Fuels
Fossil Fuels
“I’d put my money on the sun and solar energy. What a source of power! I hope we don’t have to wait until oil and coal run out before we tackle that.”
(1931) in conversation with and
• At the current rate of consumption of reasonably recoverable reserves 1, 2
• Coal reserves will run out in 130 years,
• Natural gas in 60 years,
• Oil in 40 – 50 years.
• We cannot continue to burn oil to secure long-term viability of our future, we need to conserve oil for lubricating the machines of the world for years to come
• Oil is used for lubricants, dyes, plastics, and synthetic rubber; natural gas is an important desiccant in industry and is used in ammonia, glass and plastics production; and coal products are used to make creosote oil, benzene, toluene, ammonium nitrate, soap, aspirin, and solvents.
• Oil, coal and natural gas are a precious resource that humankind cannot afford to burn anymore.
1 World Coal Institute www.worldcoal.org
2 . Of the IEEE 98 (2010) 42 – 66. 10
Nuclear Fission & Fusion
• At the current rate of consumption with conventional reactors, there are only 80 years of world uranium resources at reasonable recovery cost levels.1, 2
• Nuclear power currently only supplies about 5.7% of the world’s total energy, thus if we hypothetically supplied the whole world’s energy needs with nuclear power there would be only 5 years of supply.
• Why does it make sense for humankind to foot the risks and costs of nuclear power, for such a short-term return?
• To supply the Worlds 18.3 TW of power with nuclear fission alone would require 18,300 1 GW reactors.
• To supply the Worlds energy needs for 1 year with nuclear fusion one would require 2290 tonnes of D2 and 68,700 tonnes of Li.
• Given that Li has several competing industrial uses the viability of nuclear fusion is ≈ 100 years.
1 World Nuclear Association (www.world-nuclear.org) 2 . Of the IEEE 98 (2010) 42 – 66.
Solar Photovoltaic
Silicon photovoltaic (PV) solar cells
• 500 km x 500 km to supply 18.3 TW (World consumption)
• 0.17 g/cm2 of arsenic → 425 million tons As → (World reserves @ 3 million
• Other varieties of solar cells → rare earth metals → world reserves stretched
Concentrating solar thermal (CST)
• 500 km x 500 km to supply 18.3 TW → Low-tech → using mirrors to provide heat
• Heat → Electricity using heat engine (i.e. Steam Engine, Stirling engine etc.) . Of the IEEE 98 (2010) 42 – 66.
Solar Hydrogen Economy
• Electricity is produced using CST and PV
• Solar farms are linked by cable to desalination plants for large scale electrolysis to
produce hydrogen
• Hydrogen is used as the dominant transport fuel and for night time power use.
• In the long term a Solar Hydrogen economy makes sense, because there is so much available power
• Conversion losses can be compensated for by adding more solar collectors.
• In the long term we have no choice, but to move almost entirely to a Solar-
Hydrogen Economy
. Of the IEEE 98 (2010) 42 – 66.
“I’d put my money on the sun and solar energy. What a source of power! I hope we don’t have to wait until oil and coal run out before we tackle that.”
(1931) in conversation with and
World uses 18.3 TW of power
To sustain this we only have a finite utility time for our resources
D. Abbott, Proceedings of the IEEE, 98 (2010) 42-66.
Silicon photovoltaic (PV) solar cells
500 km x 500 km to supply 18.3 TW (World consumption)
0.17 g/cm2 of arsenic → 425 million tons As → (World reserves @ 3 million tons) Other varieties of solar cells → rare earth metals → world reserves stretched
Concentrating solar thermal
500 km x 500 km to supply 18.3 TW → Low-tech → using mirrors to provide heat Heat → Electricity using heat engine (i.e. Steam Turbine, Stirling engine etc.)
Facts about Hydrogen
• Hydrogen is the most abundant element in the universe and makes up 75 % of all known mass in the universe.
• Hydrogen is the lightest element in the universe. The hydrogen atom (H) has one proton and one electron and it exists at STP in a molecular form (H2) as a gas.
• If hydrogen is burnt with oxygen it forms water.
• Hydrogen is colorless, has no odor or taste and is non-toxic. It is highly
flammable, but will not ignite unless an oxidizer and ignition source are present.
• Hydrogen has an autoignition temperature of 585 °C in air
• The flammability range of hydrogen is between 4 – 77% H2 to air volume ratio.
• The ignition energy of hydrogen is 0.02 MJ.
Why Hydrogen?
• Hydrogen can be produced from many primary sources.
• No greenhouse gases are produced when hydrogen is used as a fuel
• Hydrogen has the highest energy to weight ratio (120 MJ/kg) of any fuel
• Hydrogen is the ideal fuel for fuel cells and can also be used in an internal combustion engine.
• Hydrogen has the potential to be a new export industry for Australia
Learning Outcome Check
Describe briefly what is meant by a solar-hydrogen economy.
List 3 advantages of using hydrogen as a fuel source, compared to the current energy mix.
Hydrogen Applications and Prospects
1. Hydrogen production 2. Utilisation
3. Distribution
4. Storage
http://css.umich.edu https://www.lbl.gov/
Electrolysis
J.O. TU Energy Technical University of Denmark (2016)
Types of electrolyzers
Fuel cells
Electrolyzer cells
Temperature
25 – 150 oC
80 oC (150 – 200 oC)
Phosphoric acid
Molten Carbonate
Solid Oxide
700 – 1000 oC
Types of electrolyzers
J.O. TU Energy Technical University of Denmark (2016) 20
The largest electrolyzers
J.O. TU Energy Technical University of Denmark (2016) 21
PEM Electrolysis
Shiva et al Materials Science for Energy Technologies 2 (2019) 442.
ITM Power HGas PEM Electrolyser
System power
H2 production rate
40 – 40,000 kg/24 h
H2 pressure
20 bar (50 bar optional)
99.5 – 99.999 %
Fuel Cells
Fuel Cell Basics Smithsonian Institute (2017) https://americanhistory.si.edu/fuelcells/basics.htm
Fuel Cells
Alkaline FC
Polymer FC
Direct methanol FC
Phosphoric acid FC
AFC 60 – 80 °C PEMFC 60 – 80 °C DMFC 60 – 80 °C
Electrolyte
aq. KOH Polymer Polymer
Molten salt Ceramic
Types of Fuel Cells
Abrev. Temp.
Low temperature systems
PAFC 200 °C High temperature systems
Molten carbonate FC MCFC 650 °C
Solid oxide FC
SOFC 700 – 1000 °C
J.O. TU Energy Technical University of Denmark (2016)
Fuel Cells
J.O. TU Energy Technical University of Denmark (2016)
Fuel Cells
J.O. TU Energy Technical University of Denmark (2016)
Fuel Cells
https://commons.wikimedia.org/wiki/File:Hyundai_Nexo_Genf_2018.jpg 28
Progress Around the Globe
$57,500 USD
$60,000 USD
DOI: 10.1016/j.pnsc.2018.03.001
500 – 700 km per tank
FCEVs fuel quickly (3 – 5 minutes) High pressure (700 bar H2 tanks)
Japan’s FCEV
2017 – 3,000 units 2020 – 40,000 units 2025 – 200,000 units 2040 – 800,000 units
http://ieahydrogen.org/pdfs/Global-Outlook-and- Trends-for-Hydrogen_Dec2017_WEB.aspx
Fuel Cells
A fuel cell electric bus is the same as a battery electric bus only with a smaller battery, hydrogen tanks and FC
Neil Thompson ITM Power – 2019 BIC National Conference
Fuel Cells
US Department of Energy – Fuel Cell Technologies Office – hydrogenandfuelcells.energy.gov
Hydrogen Refuelling Station
Hydrogen Energy Density
Hydrogen Storage
Hydrogen Storage: The best way?
Technique Compressed Gas
Liquid Hydrogen Porous Materials Metal Hydrides Complex Hydrides Hydrolysis
kg H2/m3 39.2
Mass Pressure Temperature Cost
5.4 700 25 Low
100 1 -253 Modest 4 70 -200 Modest 3 30 25 High
10 30 300 Modest 10 1 25 High
Hydrogen Storage – High Pressure
Hydrogen has an energy density of 33.33 kWh/kg.
Energy loss on compression/cooling Liquefaction – 36%
700 bar compression – 9%
Must consider energy required to store hydrogen and release it.
Learning Outcome Check
Calculate and compare the mass of different fuels required to achieve the same heating duty.
List 5 techniques used to store hydrogen. Comment on their relative temperatures and pressures, and cost.
Hydrogen Storage Research Group
Hydrogen storage for mobile and stationary applications
Thermal Batteries
Research Directions
Hydrogen Export
Solid State Electrolytes
Mobile and Stationary Applications
Vehicular Applications
Remote Energy Applications
Toyota Mirai
Phase Change Material
Metal Hydride composite
Gray et al IJHE 36 (2011) 654
for Road Transport in Western Australia – Future Energy Exports Cooperative Research Centre (CRC)
• Partners: Sustainable Built Environment National Research Centre (through its partners MRWA, BGC Australia and ATCO), Curtin University and UWA.
• 3 year project. Total Budget: $805 k.
• Review on Green hydrogen for heavy transport applications and techno-economic analysis for the deployment of the required infrastructure in WA.
• Execution of the demonstration trial including deployment of a 5 ton maintenance truck and a 29 ton concrete agitator truck operating in the Midwest and Perth regions.
• Data collection and analysis according to the defined metrics to evaluate the performance of the vehicles and refuelling stations.
Hydrogen Storage in Powders
Hydrogen Export from Australia
Hydrogen gas takes up too much volume for export.
• Liquid ammonia
• Liquid organic hydrogen carriers
• Liquid hydrogen
• Solid-state metal hydride
International Export of Hydrogen
Hydrogen carrier
Transport conditions
Volumetric density of H2 (kg/m3)
Conditions for H2 release
Gaseous H2
25 °C (100 bar)
Gaseous H2
25 °C (700 bar)
Liquid NH3
25 °C (10 bar)
Dibenzyl toluene
Solid State Hydride
25 °C in water
• Japan utilised renewable hydrogen for the 2021 Olympic Games
• Currently doesn’t have infrastructure for mass production of H2
• Australia uniquely positioned to become H2 export leader
• Australian Government and Chief Scientist have also now suggested hydrogen as a future
energy export vector to global markets
• Correct choice of export material must be made
• Dependent on conditions, volume density, H2 release and cost
A Solid State Hydride as a H2 export medium
• Key questions:
• Canwemanufacturelargequantitiesofasolidstate(SS)hydrideinAustralia? • Howwillitbetransported?
• How will H2 be released?
• Canweregenerateinhighyields?
• A regenerative cycle has been identified
Thermal Battery Research based on Metal Hydrides and Metal Carbonates
High Temperature Metal Hydrides for Concentrated Solar Thermal Energy Storage
Current Technologies
Type of thermal energy Example of TES material Total heat storage storage (TES) capacity (kJ/kg)
Sensible heat Molten salt mixtures 153 per 100°C
Latent heat / phase change materials
Thermochemical Oxidation of Co3O4 1055
Metal Hydride MgH2 → Mg + H2 2814
Energy Storage
• Most current CST systems use the simplest method, sensible heat storage, and the predominant materials used are binary (60% NaNO3; 40% KNO3) molten salt mixtures.
• Solar Millenium’s 50 MW Andasol I plant with 7.5 hours storage uses 28,500 tonnes of molten salt
CSP Stirling Dish
Stirling Engine
Solar Thermal Batteries – Hydrogen
The sun’s rays are Concentrated to generate heat
The heat is used to generate electricity
During the Day
Some of this heat is used to release hydrogen from a metal hydride and the hydrogen is stored
This heat is used to generate electricity
Hydrogen is allowed to react with the metal to form a metal hydride and release heat
Average Solar Irradiance
9 8 7 6 5 4 3 2 1 0
Broome, Australia
Carnarvon, Australia
Kalgoorlie, Australia
Perth, Australia
Port Hedland, Australia
Hamburg, Germany
Paris, France
Rome, Italy
JAN FEB MAR APR MAY JUN JUL AUG SEP OCT NOV DEC
Average Solar Irradiance (kWh/m2/day
Mining in Australia
Remote Area Power
Critical problem for remote area operations: Mining, Communities The majority of remote mines cannot be connected to the power grid All the electricity must be generated on-site
Diesel Generators – 2.2 MW each!
Remote Area Power
Electricity demand (typical mine site):
• Peak demand: 5 – 650 MW
• Fluctuating demand – peak during day
• High reliability required (auxiliary back-up is essential)
J. Paraszczak and K. Fytas, ICREPQ’12, Spain 2012
Diesel typically must be transported by trucks, adding to its consumption.
The iron ore industry
in Western Australia
consumes in excess of a 3 million litres of diesel each DAY!!!
S. S. Shastri – Australia’s Mining Thirst, GHD Perth, 2012
Diesel Usage
Diesel powered power plants 30 – 40 c/kWh
Solar thermal is more than competitive. CSP plant 13.5 c/kWh
High Temperature Metal Hydrides
Revisit high temperature materials that have been mostly overlooked
Material Temperature
YH3 > 1200 °C CaH2 >950°C LiH >900°C ZrH2 >800°C TiH2 >700°C NaMgH3 >400°C
Enthalpy (kJ/mol H2)
Q. Lai, M. Paskevicius, D.A. Sheppard, C.E. Buckley, A.W. Thornton, M.R. Hill, Q. Gu, J. Mao, Z. Huang, H.K. Liu, Z. Guo, A. Banerjee, S. Chakraborty, R. Ahuja, K.F Aguey-Zinsou. “Hydrogen storage materials for mobile and stationary applications: Current state of the art.” ChemSusChem, 8 (2015) 2789 – 2825.
D.A. Sheppard, M. Paskevicius, C.E. Buckley, M. Felderhoff, R. Zidan, D.M. Grant, M. Dornheim et al. “Metal hydrides for concentrating solar power energy storage” Applied Physics A 122:395 (2016) 1 – 15.
P.A. Ward, C. Corgnale, J.A. Teprovich Jr., T. Motyka, B. Hardy, D.A. Sheppard, C.E. Buckley, R. Zidan. “Technical challenges and future direction for high-efficiency metal hydride thermal energy storage systems” Applied Physics A 122:462 (2016) 1 – 10.
Theoretical Heat Storage Capacity (kJ/kg)
Operating Temperature (°C)
Sensible Heat
NaNO3/KNO3
153 per 100 °C
Metal Hydrides
Mg2NiH4 ←→ Mg2Ni + 2H2
MgH2 ←→Mg+H2
Mg2FeH6 ←→ 2Mg + Fe + 3H2
NaMgH3 ←→NaH+Mg+H2
NaMgH3 ←→ Na + Mg + 1.5H2
TiH1.7 ←→Ti+0.85H2
700 – 1000
CaH2←→ Ca+H2
LiH ←→ Li + 0.5H2
M. Fellet. Feature Editors C.E. Buckley, M. Paskevicius, D.A. RS Bulletin 38 (2013) 1012 – 1013. K. Manickam, C.E. Buckley et al. International Journal of Hydrogen Energy, 44 (2019) 7738 – 7745.
L. Poupin, C.E. Buckley et al. Sustainable Energy & Fuels, 3 (2019) 985 – 995.
T.D. Humphries, C.E. Buckley et al. Journal of Physical Chemistry C, 124 (2020) 5053 – 5060.
The CO2 Thermal Battery
Renewable Energy In
Stirling Engine
• Chemical reaction stores and releases heat energy
• Controlled using gas pressure
• Electricity in – Electricity out
EAT Stored
HEAT Released
OR Limestone
T.D. Humphries, C.E. Buckley et al. J. Materials Chemistry A 7 (2019) 1206 – 1215.
Thermal Battery Price
Limestone (CaCO3) is the primary ingredient $5 – 10 per tonne Literally DIRT cheap
Current Generation
Raw Material Cost
So why has this not already been done?
Catalyst Development
500 cycles90% capacity retention Catalysts are expensive…
Al2O3 is cheap! $324/tonne
J. Mater. Chem. A, 2020, 8, 9646–9653
Our catalyst
Breakthrough for Thermal Battery Lifetime
Thermochemical reaction (energy storage/release)
Catalyst formation (only occurs once)
Innovation and novelty is: working catalyst
Patent has been submitted
Optimisation and upscaling of technology in-progress
J. Mater. Chem. A, 2020, 8, 9646–9653
Patent Application No. PCT/AU2020/051393 “Thermal Battery.” K. Moller, M. Paskevicius, C.E. Buckley, Curtin University.
CaCO3 for other Applications
Waste heat in
Waste heat
Steel Making
Applied Energy 237 (2019) 708–719
The Future for Hydrogen and Thermal Batteries
• Multipleapplicationsforhydrogen=Varietyofstoragesolutions.
• Smallmobilestorage(e.g.cars)Highpressurecompressedgastanks.5kgH2at700
bar = 127.5 L.
• Medium mobile storage (e.g. trucks, buses) Gas tanks, 50 kg
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