Hydrogen Research at Curtin University

Professor Craig Buckley

Department of Physics and Astronomy

Faculty of Science and Engineering

Curtin University, WA, Australia

Acknowledgements

Dr. Mark Paskevicius, Dr. Drew Sheppard, Dr. Terry Humphries, Dr.Veronica Sofianos, Dr. Matthew Rowles, Dr. Dehua Dong, Dr. Kasper Moller

Payam Javadian, Tam Nguyen, Arnaud Griffond, Mariana Tortoza, Enrico Ianni, Kyran Williamson, Lucas Poupin

Ragaiy Zidan, Ted Motyka, Claudio Corgnale, Bruce Hardy

SRNL - US DOE Sunshot Initiative

ARC Linkage Grants LP120100435, LP150100730

Australia-China Science Research Fund

ARC LIEF Grants LE0989180, LE0775551, LE140100075

Kenneth Allen Ausnational Investments Pty Ltd

Hydrogen Research at Curtin University

Hydrogen Storage Research Group (HSRG)

Fuels and Energy Technology Institute (FETI)Hydrogen Storage, Biofuels, Fuel Cells, Batteries, Renewable Energy

Hydrogen Research: Focus on chemical storage of hydrogen in powders

Mobile Applications

Stationary Applications

Thermal Energy Storage

e.g. Cars, Trucks e.g. Fuelling Stations e.g. Concentrating SolarThermal Power Plants

Hydrogen Export

e.g. Solid-state

Hydrogen: Uses and Prospects

Hydrogen: Uses and Prospects

Hydrogen: Uses and Prospects

Hydrogen Progress Around the Globe

$57,500 USD $60,000 USD

400 – 600 km per tank

FCEVs fuel quickly (3-5 minutes)

Japan’s FCEV2017 – 3,000 units2020 – 40,000 units2025 – 200,000 units2040 – 800,000 unitshttp://ieahydrogen.org/pdfs/Global-Outlook-and-Trends-for-Hydrogen_Dec2017_WEB.aspx

High pressure (~700 bar H2 tanks)

Hydrogen Progress Around the Globe

Hydrogen Fuelling Stations

Hydrogen Progress in Japan

Electricity output: 25 kW maximumHydrogen tank storage capacity: 104 Nm3

Power supply capacity: 69 kWh

Energy Storage System

Hydrogen Progress in Japan

2020 Olympic GamesTokyo Organising Committee: “Towards Zero Carbon”

“The Tokyo Organising Committee sees the games as a testing ground for Japan’s long-term goal of realizing a hydrogen society.” [Japan Times 2018]

Push towards using ‘renewable hydrogen’ – sourced from renewable energy

Hydrogen Export from Australia

Hydrogen gas takes up too much volume for export.

Options:

• Liquid ammonia

• Liquid hydrocarbons

• Liquid hydrogen

• Solid-state metal hydride

Hydrogen Storage

Hydrogen: Uses and Prospects

Hydrogen Storage in Powders

High Pressure Gas Storage

Hydrogen Storage – High Pressure

Hydrogen has an energy density of33.33 kWh/kg.

Energy loss on compression/cooling

Liquification – 36%

700 bar compression – 9%

Must consider energy required to storehydrogen and release it.

High Temperature Metal Hydrides for Concentrated

Solar Thermal 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

Current Technologies

Type of thermal energy storage (TES)

Example of TES material

Total heat storage capacity (kJ/kg)

Sensible heat Molten salt mixtures 153 per 100C

Latent heat / phase change materials

NaNO3 282

Thermochemical Oxidation of Co3O4 1055

Metal Hydride MgH2 → Mg + H2 2814

Energy Storage

Stirling Engine

Case Study – Solar Reserve

Crescent Dunes Project - Tonopah, Nevada, U.S.A.

Project Completion – 2015

110 MW →          Enough to power ~ 75,000 houses

32,000 Tonnes of Molten Salts

10 hours thermal storage (~ 11 – 15% cost of entire project!)

Cost: $1.0 billion

CSP Stirling Dish

Australia

0

1

2

3

4

5

6

7

8

9

JAN FEB MAR APR MAY JUN JUL AUG SEP OCT NOV DEC

Ave

rag

e S

ola

r Ir

rad

ian

ce (

kWh

/m

2/

day

Broome, Australia

Carnarvon, Australia

Kalgoorlie, Australia

Perth, Australia

Port Hedland, Australia

Hamburg, Germany

Paris, France

Rome, Italy

Average Solar Irradiance

Mining in Australia

Remote Area Power

Diesel Generators – 2.2 MW each!

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

Remote Area Power

Diesel typically must be transported by trucks, adding to its consumption.

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

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. Crescent Dunes 13.5 c/kWh

The sun’s rays are Concentrated

to generate heat

The heat is used togenerate electricity

Some of this heat is used to release hydrogen froma metal hydride and the hydrogen is stored

This heat is used togenerate electricity

Hydrogen is allowed to react with the metal to form a metal hydride and release heat

At Night

During the Day

Solar Thermal - Hydrogen

High Temperature Metal Hydrides

Material Temperature Enthalpy (kJ/mol H2)

YH3 > 1200 °C 220 CaH2 > 950 °C 208 LiH > 900 °C 134 ZrH2 > 800 °C 212 TiH2 > 700 °C 164 NaMgH3 > 400 °C 87

Revisit high temperature materials that have been mostly overlooked

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.

MaterialsTheoretical

Heat Storage Capacity (kJ/kg)

Operating Temperature

(°C)

Sensible HeatNaNO3/KNO3 153 per 100°C 290 - 565

Metal HydridesMg2NiH4 ←→ Mg2Ni + 2H2 1158 250 - 400

MgH2 ←→ Mg + H2 2811 300 - 400Mg2FeH6 ←→ 2Mg + Fe + 3H2 2096 350 - 550

NaMgH3 ←→ NaH + Mg + H2 1721 430 - 585

NaMgH3 ←→ Na + Mg + 1.5H2 2881 > 585

TiH1.7 ←→ Ti + 0.85H2 2842 700 - 1000CaH2 ←→ Ca + H2 4934 >1000LiH ←→ Li + 0.5H2 8397 >850

M. Fellet. Feature Editors C.E. Buckley, M. Paskevicius, D.A. Sheppard MRS Bulletin 38 (2013) 1012 – 1013.

Thermodynamics

STHG

0

ln eqf H Sf RT R

0

1ln dp

mVf pp RT p

G Gibbs free energy

H Enthalpy

S Entropy

f Fugacity

P Pressure

Vm Molar volume

T Temperature

f0 Reference fugacityof 1 bar

Thermodynamics

The relationship between pressure‐composition (P‐C) isotherms (left) and the van't Hoff plot (right) in which thermodynamic data is determined. Fugacity values (Feq) correspond to equilibrium plateau pressures measured at constant temperature T. Tc is the critical temperature above whichno equilibrium plateaus are observed.  Adapted from M. Latroche, Journal of Physics and Chemistry of Solids, 65 (2004) 517‐522.

Efficiency and Hysteresis

G. Sandrock, State-of-the-Art Review of Hydrogen Storage in Reversible Metal Hydrides for Military Fuel Cell Applications, in, Department of the Naval Office of Naval Research, 1997.

Carnot Efficiency = 1 – TC /TH

Practical Efficiency = 1 – (TC /TH)1/2

Costs

Total Installed Cost

Electrical Energy Required LT H2 wt.%

Mass of H2Required

Thermal Energy Required

Thermal StorageCapacity

Amount of HT Hydride

HT RawMaterials Cost 

Amount of LT Hydride

LT RawMaterials Cost 

HT H2 wt.%

HT H

Operating Temperature& Efficiency

Cost of HT Hydride

Cost ofLT Hydride

LT Engineering CostHT Engineering Cost

Fluorine substitution in NaMgH3 NaMgH2F

Can we increase the enthalpy of NaMgH3 by fluorine substitution?

fHo (NaMgH3 @298 K) = - 231 kJ/molfHo (NaMgF3 @298 K) = -1716 kJ/mol

NaMgH3 and NaMgF3 form a complete solid solution series Stability of NaMgH2F > NaMgH3?

The rationale - To explore new low-cost, HT hydrides for solar thermal storage.- Operating temperatures above 650 oC are preferable.

D.A. Sheppard, M. Paskevicius, C.E. Buckley, Chemistry of Materials 23 (2011) 4298 – 4300.D.A. Sheppard, T.D. Humphries, C.E. Buckley, Materials Today 18 (2015) 414 – 415.

Addition of F partially decreases theequilibrium pressure at the expense ofH2 wt.%.

NaMgH3 vs NaMgH2F Two-step < 478 oC < Single-step

PCT Measurements

Sheppard Buckley et al., RSC Advances, 4 (2014) 26552 - 26562.

Thermodynamics and Thermal Storage Capacity

NaMgH2F • Theoretical H2 capacity of 2.95 wt.%.• H ~ 96.8 kJ/mol.H2 above 478oC.• Thermal storage capacity of 1416 kJ/kg.

NaMgH2F has the lowest thermal storage capacity compared to other well studied Mg-based hydrides.

BUT…

Mg-based HT Hydrides: A Case Study on Costs

Cost Estimates for:

• 200 MW power plant with MgH2, Mg2FeH6, NaMgH3 or NaMgH2F as HT hydride.

• 7 h of thermal storage at full load.

• The operating temperature range for Mg2FeH6, NaMgH3 and NaMgH2F was chosen so that each of the systems had comparable hydrogen operating pressures.

• MgH2 temperature limited to 400oC to avoid sintering effects.

• Low-cost LT Hydride of Ti1.2Mn1.8 with 1.9 wt.% H2 capacity.

• Efficiency of power generation based on Practical Carnot Efficiency1.

• Engineering costs estimated for pressure vessels and heat exchangers2.

1 R.F. Boehm, Applied Energy, 23 (1986) 281-296. 2 K.M. Guthrie, Chem Eng Progr, (1969) 114 – 142.

Mg-based HT Hydrides: A Case Study on Costs

- In all cases, the LT hydride cost is significant.

- Despite the lower thermal capacity, NaMgH2F has the lowest overall installed cost.

- The higher operating temperature and Hreduces the quantity of H2 and LT metal.

- These factors also reduce the engineering and heat exchanger costs.

Sheppard Buckley et al., RSC Advances, 4 (2014) 26552. Lai Buckley et al., ChemSusChem 8 (2015) 2789

Hydride Thermal Energy

Required(MWhth)

Mass of H2

(tons)

Mass of HTMH(tons)

Mass of LTMH(tons)

Cost of HTMH

(M $US)

Cost of LTMH

(M $US)

Cost of HTMH + LTMH +

ENG(M $US)

Cost of HTMH + LTMH +

ENG($US/kWhth)

Total cost of system

(includes estimate of

Engineering & containment)($US/kWhth)d

Total cost of system(M $US)

MgH2 4033 325 5995 17087 19.79 123.96 143.75 35.64 47.08 189.9

Mg2FeH6 3451 247 5465 12979 10.92 94.15 105.07 30.45 41.54 143.3

NaMgH31st Step

3063 191 6423 10067 21.76 73.03 94.79 30.95 42.86 131.3

NaMgH2F 2890 196 8671 10296 17.38 74.70 92.08 31.86 45.42 131.3

• Cost of molten salt raw materials (60 wt.% NaNO3 and 40 wt.% KNO3) ranges from 0.62 – 0.77 $US/kg. Total cost 19.7 – 24.4 M $US.

• The cost of thermal storage system at Crescent Dunes (including molten salts, engineering, containment, pumps etc.) range from 30 - 40 $US/kWhth

1. Total cost of the molten salt heat storage system 110 – 150 M $US.

• Molten Salts 73 - 97 $US/kWhel. All of the hydrides except MgH2 range from 92 – 101 $US/kWhel.

• NaH/NaAlH4 54 $US/kWhel. NaMgH3/NaAlH4 74 $US/kWhel2.

1 Engineering Economic Policy Assessment of Concentrated Solar Thermal Power Technologies for India, Dec 2012.2 Corgnale et al. Renewable and Sustainable Energy Reviews 38 (2014) 821 – 833.

Comparison of Hydride and Molten Salt Thermal Storage

Compressed H2 Gas

• LT hydride is the largest cost component of the coupled system (50 – 90% of the cost)

• During absorption the LT hydride is exothermic – this heat needs to be removed.

• During desorption the LT hydride is endothermic. Heat must be added.

• Compressed gas maybe a much cheaper option

• Ideally we require a high T hydride with lowest cost, highest enthalpy of absorption, highest operating T and highest operating P.

• Containment of high P & T H2 is a difficult engineering problem.

Destabilisation of LiH

Change the H2 reaction, and cost, by the addition of a second element. 

Destabilisation of LiH: • Pure system: 2LiH + H↔2Li + H2 956oC for 1 bar H2

• Destabilised system:  2LiH + 2Al + H↔2AlLi + H2 ?? for 1 bar H2

How do the properties change?

H2 Capacity (wt.%)

H(kJ./mol.H2)

1 bar H2Equilibrium Temp. (oC)

Heat Storage Capacity (kJ/kg)

Cost (US$/kg) US$/kWhth

LiH Theor. 12.68 133.5 956 8397.3 61.12 26.23Pract. 7.61 133.5 956 4198.6 61.12 52.46

LiH+Al Theor. 2.89 96.8 573 1412.5 13.51 35.12Pract. 2.06 96.8 573 1150.3 13.51 49.20*Pract.  2.06 96.8 573 1888.1 13.51 29.51

* Includes heat capacity and melting  for 565oC < T < 710oC of AlLi.P. Javadian, D.A. Sheppard, T.R. Jensen, C.E. Buckley. RSC Advances 6 (2016) 94927 – 94933.

Physical Properties of Selected High Temperature Hydrides

1 2 3 4 5 6 7 8 9 10 11 12

Material T ( C) P(bar)

T ( C) P(bar)

Enthalpy (H) kJ/mol

H2

Thermal StoragekJ/kg

(Practical)

(Density)

Kg/m3

Thermal Energy Density

kWhth/m3

Cost HTMH

$US/kg

Cost HTMH$US/kWhth

Cost HTMH + LTMH

$US/kWhth

A 788 1 850 5 120.0 1238 2466 848 0.91 2.65 8.75

B 476 1 650 55 132.5 1704 2028 960 0.59 1.25 6.77

C 567 1 800 9 107.8 943 2279 597 2.11 8.05 14.84

D 708 1 800 3.1 107.3 632 2001 353 2.26 12.86 19.68

E 486 1 700 61.6 83.1 735 2286 466 1.967 9.65 18.47

2CaMgNiH4 2CaH2 + Mg + MgNi2 + 2H2

411 1 600 136 129 863 2770 664 12.03 50.22 55.90

TiH1.0 + 0.3H2 TiH1.6(Pure Ti)

632 1 850 50 165.3 851 3810 901 19.75 83.52 87.95

TiH1.0 + 0.3H2 TiH1.6(Ti sponge)

632 1 850 50 165.3 851 3810 901 7.9 33.41 37.84

NaMgH3 NaH + Mg + H2 400 1.53 480 7.9 86.6 1463 1460 593 3.0 7.38 15.84

Mg2FeH6 2Mg + Fe + 3H2 304 1 564 150 77 1777 2740 1352 2.5 5.07 14.57

MgH2 Mg + H2 282 1 400 17 74 2389 1450 962 2.9 4.37 14.26

NaH Na + 0.5H2 427 1 600 53 117 2072 1396 803 4.0 6.95 13.21

HTMH – High temperature metal hydrideLTMH – Low temperature metal hydride

The Future of Hydrogen (Storage) in WA

Multiple applications for hydrogen = Variety of storage solutions Small mobile storage (e.g. cars) High pressure compressed gas tanks

5 kg H2 at 700 bar = 127.5 L Medium mobile storage (e.g. trucks, buses) Gas tanks or solid-state storage

50 kg H2 at 350 bar = 2150 L Large scale stationary storage (e.g. fuel station, heat storage) Gas tanks or solid-state storage

Is volume an issue? Solid-state costs more, but output pressure is controllable

Hydrogen will move forward in WA as a energy carrier. It needs to be paired with renewables so that it carries ‘clean’ energy.

Hydrogen can be used in WA as a fuel or exported as an energy export industry. Hydrogen in metal hydrides can be used for heat storage to produce electricity 24/7 Some technical challenges to improve technology cost / efficiency / performance

However, hydrogen can be used today!

AN INTERNATIONAL ENERGY AGENCY TECHNOLOGY COLLABORATION PROGRAMME

Australian Association of Hydrogen Energy (AAHE)

• Formed in 2009 as the National Association promoting the use of hydrogen as an energy carrier

• Role to co-ordinate representation of hydrogen energy interests in Australia

• New Website under construction at present time

• Membership can be applied for from present website

• Present website can be accessed with up to date global hydrogen energy developments

www.hydrogenaustralia.org

Thanks for Listening

Any Questions?

Conclusions

• Solar Energy will be the dominant solution for the long term future

• Concentrated Solar Thermal (CST) with storage has the potential to provide base load power

• CST should be used in more remote locations now

• Molten salt storage is the first generation storage system for CST

• Metal hydrides have the potential to be the next generation storage system for CST

Hydrogen Permeability

D. L. Hanson, Test Plan for Characterizing Tritium Transport in a VHTR, PC-000550-0, General Atomics, San Diego, CA, December 20, 2007.

Δ

Fluxarea-normalized volumetric flow rate

Permeability

Thickness

Pressure

H2

Test Material: H2 Desorption Measurements on TiH1.6

Measured Thermodynamics@ H/M = 1.2R2 = 0.9998H = 165.8 kJ/mol H2S = 182.9 J/mol H2.K

Average Literature ValuesH = 165.5 kJ/mol H2S = 180.2 J/mol H2.K

567

1

2

3

4567

10

2

3

H2 D

esor

ptio

n Eq

uilib

rium

Pre

ssur

e (b

ar)

1.61.41.21.00.80.6H/M Ratio

724.5oC 701.4oC 689.7oC 672.7oC 652.2oC

Plateaux slope expected due to impuritiesBUT

Plateau Slope:SiC = 0.36‐0.38Al‐coated  = 0.47‐0.54

↓H2 permeation through SS‐316 end cap

Al coated

Hydrogen Permeation at High Temperatures

Where to?Lab-Scale Prototype (10’s of grams)

Heat

Hydrogen

Furnace:Simulating Solar Cycle

High TempHydride

Low TempHydride

Heat Engine

24 h operation

Lab-Scale Prototype

Paskevicius, Sheppard, Williamson, Buckley. Energy 88 (2015) 469

Metal Hydrides for Low Temperature Storage

Compound H2 WT.% CAPACITY

Hydrogen equilibrium pressure at 25 °C (bar)

Plateau slopeΔln(Pabs)/Δ(H2 content)

Hysteresisln(Pabs/Pdes)

Minimum mass required (kg) for 140

kg of H2 storage

Raw material cost (USD)

TiFe 1.9 4.1 0 0.64 7,496 51,000TiFe0.8Ni0.2 1.3 0.1 0.36 0.05 10,730 103,000TiFe0.9Mn0.1 1.9 2.6 0.92 0.62 7,341 51,000V 3.8 2.1 0.15 0.2-0.7 3,660 1,445,000(V0.9Ti0.1)0.95Fe0.05 3.7 0.5 0.45 0.8 3,770 1,279,000LaNi5 1.5 1.8 0.13 0.13 9,362 580,000LaNi4.7Al0.3 1.4 0.42 0.48 0.05 9,685 604,000CaNi5 1.2 0.5 0.19 0.16 11,626 276,000TiCr1.8 2.4 182 0.12 0.11 5,742 82,000TiMn1.5 1.9 8.4 0.57 0.93 7,496 58,000

Ti0.98Zr0.02V0.48Fe0.09Cr0.05Mn1.5 1.9 11 1.1 - 7,341 453,000

NaAlH4 ↔ Na3AlH6 3.7 0.7 Negligible Negligible 3,739 14,000

D.N. Harries, M. Paskevicius, D.A. Sheppard, T. Price, C.E. Buckley, Concentrating solar thermal heat storage using metal hydrides’, Proceedings of the IEEE 100 (2012) 539 - 549.

Pottmaier, et al. Chemistry of Materials 2011 23 (9), 2317-2326

NaMgH3

Ikeda et al., J. Alloys Compd., 446-447 (2007) 162-165.

Komiya, et al., J. Alloys Compd., 453 (2008) 157-160.

Thermodynamics for the 1st Desorption Plateau: Problems?Source Reported ΔH

(kJ/mol H2)Reported ΔS (J/mol H2/K)

Actual ΔH (kJ/mol H2)

Actual ΔS (J/mol H2/K)

Ikeda et al. 1 93.9 116.2 74.2 113.6Komiya et al. 2 94 140 94.4 141.1Pottmaier et al. 3 92 123 95.7 146.1

NaMgH3 NaH + Mg + H2NaH Na + ½ H2

Pottmaier, et al. Chemistry of Materials 2011 23 (9), 2317-2326

NaMgH3

D.A. Sheppard, M. Paskevicius, C.E. Buckley, Chemistry of Materials 23 (2011) 4298 – 4300.

Hysteresis?

ThermodynamicsH = 86.6 kJ/mol.H2S = 132.2 J/mol.H2.K

Thermodynamic data for NaMgH3

Source Temperature (K)

Reported ΔH (kJ/mol H2)

Reported ΔS (J/mol H2/K)

Est. Eq. Press. (bar)

Recalculated ΔH (kJ/mol H2)

Recalculated ΔS

(J/mol H2/K)

Ikeda et al. 1 653 93.9 116.2 1 74.2 113.6673 1.5693 2.2

Komiya et al. 2 673 94 140 1.15 94.4 141.1698 1.9723 3.7

Pottmaier et al. 3 650 92 123 0.3 95.7 146.1670 0.9680* 1.9700* 3.1723* 5.2

This Work 4 671.45 - - 1.471 86.6 132.2683.85 1.965691.95 2.355702.85 2.964712.05 3.559

1. Ikeda, K.; Kato, K.; Shinzato, Y.; Okuda, N.; Nakamori, Y.; Kitano, A.; Yukawa, H.; Morinaga, M.; Orimo, S., J. Alloys and Compounds 446-447, (2007) 162-165.2. Komiya, K.; Morisaku, N.; Rong, P.; Takahashi, Y.; Shinzato, Y.; Yukawa, H.; Morinaga, M., J. Alloys and Compounds 453 (2008), 157-160.3. Pottmaier, D.; Pinatel, E. R.; Vitillo, J. G.; Garroni, S.; Orlova, M.; Baro, M. D.; Vaughan, G. B. M.; Fichtner, M.; Lohstroh, W.; Baricco, M., Chemistry. of Materials. 23 (2011), 2317-2326.4. D.A. Sheppard, M. Paskevicius, C.E. Buckley, Chemistry of Materials 23 (2011) 4298 – 4300.