DBook-AllEnergy-Aberd-21May13-v3 copy

Materials for Hydrogen
Storage & Separation
H2FC Supergen Hydrogen and Fuel Cell Hub meeting
All-Energy, AECC, Aberdeen, 21 May 2013
Dr David Book
School of Metallurgy and Materials
University of Birmingham
Birmingham, UK
[email protected]
www.hydrogen.bham.ac.uk
Dr David Book, Dr Allan Walton, Prof Rex Harris, Dr John Speight, Dr Dan Reed,
Dr Shahrouz Nayebossadri, Simon Cannon
Dr Steven Tedds, Dr Sean Fletcher, Dr Alex Bevan, Dr Vicky Mann, Dr Yinghe Zhang,
Dr Ruixia Liu
• Lydia Pickering, Sheng Guo, Naser Al-Mufachi, Luke Hughes, Joshua Vines, Yinghui Liu,
Xiaodong Yi, Yuecheng Yi, Richard Wyse
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Hydrogen Separation
• “Pd membranes provide < 1 ppb purity with any gas quality” - JM
• PEM Fuel Cells are poisioned by: CO > 10 ppm, and Sulphur at ~1 ppb
• Combined hydrocarbon reformation / separation reactors
Identical specimens of
palladium (left) and
palladium-silver (right)
after 30 thermal cycles in
hydrogen
G.J. Grashoff et al, Platinum Metals Rev., 27, (4) pp.157-169, 1983
Membrane Gas Separation Test Rig
Gas Mixture
Control (4x
MFC)
Exhaust & Pressure
Release Control (2x
MFC)
Split
Furnace
Mass
Spec
Inlets
Membrane
Inconel
Furnace Tube
Temperature,
Pressure & Flow
Control
Mass Spectrometer
Vacuum Pump
Ternary Pd-Based Alloys
6.00E-008
Pd-Y8
Pd-Ag-X
5.00E-008
4.00E-008
-1
-1
Permeability (mol m s Pa
-0.5
)
All compositions in at%
Pd-Ag24
3.00E-008
2.00E-008
Pd-Cu53
Pd-Cu-X (FCC)
1.00E-008
Pd
Pd-Cu48 (FCC)
0.00E+000
50
100
150
200
250
300
350
400
450
o
Temperature ( C)
S. Fletcher, S. Nayebossadri, J.D. Speight, I.R. Harris, D. Book, To be published
500
5 µm Pd alloy
Surface-treated
layer
Magnetron Sputterer
• Process developed to allow defect-free Pd-based thin-film
deposition onto porous stainless steel substrates
HYPNOMEM project (with Teer Coatings)
Sean Fletcher, PhD Thesis, University of Birmingham (2010)
Thin-film / Porous Stainless Steel Composites
As Received
Surface Treated
Surface optimized for thin film deposition – with cracks
HYPNOMEM project (with Teer Coatings)
Sean Fletcher, PhD Thesis, University of Birmingham (2010)
Melt-spinning
Amorphous Transition Metal-based alloys
for H2 separation membranes
charging still requires 30 minutes to deliver 13 kWh using a 40-kW, high-power electric
charger, although this reduces battery life. In addition, charging at 40 kW could have a
significant impact on the grid. Hydrogen fuel cell storage systems have a mass of about
125 kg and can be refilled within three-to-five minutes, providing another EV option if quick
refueling and longer driving range are required.
Hydrogen Storage
Weight of energy storage systems to take a car 500 km
Figure
– Vienna
WeightMotor
and volume
of energy
storage
systems
for a 500-km vehicle range.
33rd6Int
Symp. 2012,
N. Brinkman
et al
(GM Europe)
Bild 6 – Gewicht und Volumen des Energiespeichersystems für eine Reichweite von
§  Major car companies intend to start manufacturing hydrogen fuelcell vehicles (2015-2017)
§  Challenges, include:
§ 
§ 
§ 
§ 
refueling station networks
large-scale, low-cost, low-carbon H2 production
cost of vehicles
on-board storage – still too bulky
e.g. Series production of Hyundai ix35 fuel cell electric vehicle (FCEV) beginning
100 kW fuel cell, 24 kW Lipolymer battery, top speed of
160 km/h (100 miles/h), and a
range of 588 km (365 miles).
Fuel Cell Today, 16 Jan 2013
4 kg hydrogen
Louis Schlapbach &
Andreas Züttel,
NATURE, 414, p.353,
(2001)
26l
33l
57l
Mg2FeH6
LaNi5H6
H2 (liquid)
110l
H2 (200 bar)
The volume of
compressed hydrogen
tanks can be greatly
reduced by using
metal hydride powders
Andreas Züttel, Switzerland, 23/05/2013
Hydrogen Storage
complex hydrides
porous
Magnesium
Carbon
Nano-Graphite
LaNi5
V-Mn
metal hydrides
XRD and Raman
www.hydrogen.bham.ac.uk
H2 Storage Measurements
www.hydrogen.bham.ac.uk
H2 Storage Measurements
www.hydrogen.bham.ac.uk
H2 Storage: (1) Metal hydrides
ZrMn1.5
Arc-melted alloy
0 sec (vacuum)
15 sec (8 bar H2)
20 sec (8 bar H2)
60 sec (5 bar H2)
Andreas Züttel (EMPA, Switzerland), 2008
Metal hydride stores –
Demonstrators at the
University of Birmingham
30 kg of LaNi5. à 5000 Ltrs of H2
MH store, in PEM-FC UPS
MH store, in PEM-FC
Portable Power
“Hydrogen, magnets, sustainability,
and industrial heritage:
the Ross Barlow canal boat”
Ingenious Project: May 2013- May 2014
Prof Rex Harris
[email protected]
PCT Measurements LaNi5 and Ti0.5V1-xTMxMn
100 11.5 90 11 80 ∆H -­‐25.05 kJ/mol H2
10.5 10 LaNi5
60 LnP Pressure (bar) 70 50 40 9.5 TiVMn
9 8.5 30 20 8 10 7.5 0 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 ∆H -­‐30.63 kJ/mol H2
7 0.00295 0.003 0.00305 0.0031 0.00315 0.0032 0.00325 0.0033 0.00335 Capacity (wt%) PCI plot at 30 °C under 100 bar H2
(Lydia Pickering et al, JALCOM, In Press, 2013)
http://dx.doi.org/10.1016/j.jallcom.2013.03.208
1/T van’t Hoff plot for hydrogen
desorption
Pressure (bar)
Metal Hydride Compressor Principle
H2 absorption
endothermic
H2 desorption
exothermic
Hydrogen Concentration (H/M)
PCI plot showing temperature
Two stage metal hydride compressor
(Lydia Pickering, Alex Bevan et al, to be published, 2013)
Metal hydride compressor 2-stage (AB5 and AB2 tanks)
automated compressor
Pressure
Temperature
Hydrogenation Sample Cell
• 700 bar H2 and 650°C
Time (min)
(Lydia Pickering, Alex Bevan et al, to be published, 2013)
Engineering Safe and Efficient HydrideBased Technologies
(Sept 2013 – 2017)
o  Small, safe and energy
efficient hydrogen refueller
that can be installed in a
domestic garage or
industrial warehouse
o Metal hydride store
o Metal hydride
compressor
Gavin Walker (PI)
David Grant
David Book
Photo adpated from image on
http://money.cnn.com.ezproxyd.bham.ac.uk/galleries/2007/biz2/0701/gallery.8greentechs/
Weeratunge Malalasekera
H2 Storage: (2) Magnesium
Magnesium can store 7.6 wt%
hydrogen, but needs to be heated to
~300°C and H2 sorption is slow
Mg/TM/Mg… multilayers
Michael Hirscher, EuroNanoforum, Trieste, Dec 2003
TEM: Mg-alloy showing mixed crystalline
and nanocrystalline regions (Warwick Uni)
H2 absorption in 10 bar – however kinetics are slow (hours)
Metallurgy & Materials
3.5 wt% at 110 °C & 2.2 wt% at 25 °C
Xiaodong Yi, Allan Walton, David Book, submitted for publication, 2013
Confocal Laser Microscopy of Pd film (65 nm) deposited onto glass
10th desorption cycle
Y. Pivak et al, Scripta Materialia, 60(5), pp.348-351, 2009
Shows the importance of the substrate-film interaction
Sputtered Mg films
As deposited
After H2 desorption
Luke Hughes et al, MH2012, Kyoto, Oct 2012
• Hydrogen desorption studies on Mg & Mg-alloy films
(with 10 nm Pd cap), using RGA and in situ XRD
H2 Storage:
(3) Borohydrides
COMPLEX
HYDRIDES
+
-
• High intrinsic hydrogen content
• Poor reversibility or irreversible
• Slow H2 sorption kinetics
25
Examples:
NaAlH4
Mg(AlH4)2
LiBH4
Mg(BH4)2
Al(BH4)3
Andreas Züttel, University of Fribourg, 15.12.2002
+
-
Zinc
Borohydride
D. Reed, PhD thesis, Birmingham, 2010
Lithium Borohydride
A. Züttel et al, J. of Power Sources 118, p.1, 2003
Borohydrides
• A series of new Zn- and Mn-based compounds have been synthesized.
No reversibility, but could have potential in reactive hydride composites.
• In situ XRD and Raman techniques developed to help characterize
reaction pathways in complex hydrides, e.g. in situ Raman of LiBH4
500
T
°C
Li2B12H12
Li2B12H12
LiBH4
a-B
400
300
200
100
Dan Reed, David Book
800
1000
Raman Shift (cm-1)
1200
Able to identify in situ intermediate amorphous phases
à help design complex hydrides that re-absorb H2 more easily
D Reed, D Book, “Recent applications of Raman spectroscopy to the study of complex hydrides
for hydrogen storage”, Current Opinion in Solid State and Materials Science 15, pp.62-72, 2011
High-pressure Raman
spectroscopy system
Gas control
100 bar cell
Y → YH3
300°C
Novel Complex Metal Hydrides for Efficient and
Compact Storage of Renewable Energy as
Hydrogen and Electricity (ECOSTORE) Starts Oct 2013
HZG, Germany
IFE, Norway
Aarhus Uni, Denmark
UNITO, Torino, Italy
CNRS, Paris, France
Birmingham Uni, UK
Geneva Uni, Switzerland
WWU, Münster, Germany
NCSRD, Greece
Zoz, Germany
SAFT, France
Rockwood Lithium, Germany
Kyushu Uni, Japan
Tohoku Uni, Sendai, Japan
H2 Storage: (4) Ball-milled graphite
u  10 wt% H2 absorbed in Graphite-0.5wt%Fe (but v. high desorption temp)
u  Optimized milling conditions for high H2 content, with no CH4 release
u  Investigating composites, for reversibility & reduced desorption temp
Yinghe Zhang, David Book, JPCC, 2011
Yinghe Zhang, David Book, Int. J. Energy Research, 2011
H2 Storage: (5) Porous Materials
MOF Cu-BTC
77 K
131 K
Variable-temperature adsorption
isotherms measured for a range of
porous materials
S. Tedds, A. Walton, D. Broome, D. Book, “Characterisation of Porous Hydrogen Storage
Materials: Carbons, Zeolites, MOFs and PIMs”, Faraday Discussions 151, pp.75-94, 2011
CL4W project
A
Hyperaccumulator
plants to extract
metals
Biog
(February 2013 – 2016)
B
Nanocatalysts for
hydrogen energy
applications
Simon de Corte et al., Microbial Biotech.
5(1), pp.5-17, 2012
10.1111/j.1751-7915.2011.00265.x
Advanced
biomass
processing
500 nm
Engineered bacteria to
produce nanometals
(e.g. PGMs)
Summary
q  Dense-metal membranes for H2 separation:
q  new Pd alloys and thin-film processes
q  non-Pd amophous materials
q  New metal hydride (MH) alloys developed
q  MH compressor
q  MH stores for stationary & marine stores
q  Room-temp H2 absorption in nano-Mg alloys
q  New borohydride compounds produced
q  In situ Raman spectroscopy (100 bar)
q  Graphite-based materials absorb 10 wt% H2
q  Characterise gas adsorption: porous materials
q  Sustainable PGM nanoparticles