development of an internal reforming alcohol high ...pem fuel cell stack irafc, jti-fch-ju-2008-1...
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Development of an Internal Reforming Alcohol High Temperature
PEM Fuel Cell Stack
IRAFC, JTI-FCH-JU-2008-1
Brussels, November 10th 2010
Project acronym: IRAFC
Grant agreement No.: 245202
Duration : Jan 2010- Dec 2012
A project supported by the Fuel Cells and Hydrogen Joint Undertaking
Project Overview – Participants Project Overview – Participants
• Advanced Energy Technologies (Coordinator), Patras, Greece
• University of Maria Curie- Sklodowska, Poland
• Nedstack Fuel Cell Technology BV, The Netherlands
• Centre National de la Recherche Scientifique, CNRS,
Strasbourg, France
• Foundation for Research and Technology, Hellas-
Institute of Chemical Engineering & High Temperature
Chemical, Patras, Greece
• Institut für Mikrotechnik Mainz GmbH, Mainz, Germany
Work Packages Work Packages
•WP1: Project Management
•WP2: Synthesis and characterization of novel high temperature polymer
electrolyte membranes
•WP3: Reforming catalysts: synthesis and screening
•WP4: Catalytic formulations into functional structures
•WP5: Electrochemical characterization of materials
•WP6: Single cell, stack design and testing
•WP7: Construction, long term testing of short stacks and integration of a 100W stack
to a complete system
•WP8: Dissemination and public awareness
The increase of the operation temperature opens new ways of direct combination of the Fuel Cell with the Reformer
Integrated reformed alcohol (methanol) HT-PEMFC configuration. The fuel cell is composed of a membrane electrode assembly (MEA)
comprising a high-temperature protonconducting electrolyte membrane sandwiched between the anodic (methanol reforming catalyst
for the production of CO-free hydrogen + anode electrocatalyst) and cathodic gas diffusion electrodes.
Graphite
Plate
Flowfield
H+
H+
H+
H+
HT-Polymer
Electrolyte
Membrane
oxygen
water
methanol
& water
carbon dioxide
& water
OHH
O
O
OHH
OHH
C
O
O
H C O
H
H
H
Al Plate
Current
Collector
Anode: Pt/C
H2→2H++2e-
Cathode: Pt/C
0.5O2+2H++2e-→H
2O
CuMnO/Cu foam catalyst
CH3OH+H
2O→3H
2+CO
2
Internal Reforming Methanol Fuel Cell
Graphite
Plate
Flowfield
H+
H+
H+
H+
HT-Polymer
Electrolyte
Membrane
oxygen
water
methanol
& water
carbon dioxide
& water
OHH
OHH
O
O
O
O
OHH
OHH
OHH
OHH
C
O
O
C
O
O
H C O
H
H
H
H C O
H
H
H
Al Plate
Current
Collector
Anode: Pt/C
H2→2H++2e-
Cathode: Pt/C
0.5O2+2H++2e-→H
2O
CuMnO/Cu foam catalyst
CH3OH+H
2O→3H
2+CO
2
Internal Reforming Methanol Fuel Cell
Main Idea Main Idea
Proof of conceptProof of concept
I-V and long term stability measurements of the TPS® type MEA
Polymer Electrolytes and Non Noble Metal Electrocatalysts for High Temperature PEM Fuel Cells,
NMP3-CT2006-033228-Apollon B
18100 18200 18800 19000 19200
0
3
6
9
12
15
Feed 2 to anode
(I = 1.7 A at 0.5 V)
Anode
feedstream (Feed 2)
(cell bypass)
Feed 2 to anode
(EOCV = 0.990 V)
t = t0
CO2, H
2
H2O
H2O
CH3OH
CH3OH
CO2
Rate, cm
3/m
in
Time, s
H2
0 50 100 150 200 250 300 350 400
0
200
400
600
800
1000
0
25
50
75
100
125
150
FEED 3
FEED 2
Power density, mW/cm
2
6.5% CH3OH (FEED 1)
13.0% CH3OH (FEED 2)
20.0% CH3OH (FEED 3)
H2O/CH
3OH = 1.5
Tcell= 200
oC
Voltage, mV
Current density, mA/cm2
FEED 1
Proof of conceptProof of concept
Performance of IRAFC.
G. Avgouropoulos, J. Papavasiliou, M. K. Daletou, J. K. Kallitsis, T. Ioannides, S. Neophytides
Applied Catalysis B: Environmental 90 (2009) 628–632
Project goalsProject goals
The ultimate goal of the project is to deliver:
-An Internal-Alcohol-Reforming High-Temperature PEM fuel cell
(IRAFC) with the following characteristics:
(i) 0.15 W/cm2 at 0.7V, operating at 220°C
(ii) Specific (W/kg) and volumetric (W/m3) power density similar to current,
state-of-the-art high-temperature PEM fuel cells operating on hydrogen.
(i) New polymer membranes with improved thermal and chemical stability
able to operate at 220°C
(ii) New alcohol reforming catalysts with improved activity and stability
able to provide stable hydrogen production in the anode environment
(iii) Bipolar plates specifically designed under the requirements of IRAFC
operation.
How to get there How to get there
Critical components of the IRAFC
Characterization of the resulting copolymers by thermal, mechanical analyses andevaluation of their phosphoric acid uptake.
Synthesis of linear aromatic Synthesis of linear aromatic polyetherspolyethers containing side pyridine, containing side pyridine,
terpyridineterpyridine or carboxyl ester unitsor carboxyl ester units
Copolymers with expected increased acid doping ability Copolymers with expected increased acid doping ability
& potential crosslinking sites.& potential crosslinking sites.
R
R
O Y O( )
R = Crosslinking SitesR = Crosslinking Sitespyridine, terpyridine or carboxyl ester units
Y : O=P-Ph, SO2
O Y O( )x 1-x
New diol monomersNew diol monomersExisting monomersExisting monomers
pyridine or tetramethyl bearing monomers
WP 2 : Synthesis And Characterization Of Novel High Temperature Polymer Electrolyte MembranesWP 2 : Synthesis And Characterization Of Novel
High Temperature Polymer Electrolyte Membranes
COOH
COOH
COOH
COOH COOH
COOH
=
N
HN
NH
N
NH2
NH2NH2
NH2
+
H2N NH2
H2N
NH2
OH2N NH2
H2N NH2NH2
NH2NH2
NH2
=
Attempts of crosslinking through Attempts of crosslinking through
ImidazoleImidazole FormationFormation
WP 2 : Synthesis And Characterization Of Novel High Temperature Polymer Electrolyte MembranesWP 2 : Synthesis And Characterization Of Novel
High Temperature Polymer Electrolyte Membranes
o Monomer Preparationo Polymerization via polycondensationo Characterization via H-NMR, GPC, DMA,TGA, FT-iR, Tensile testingo Selection of the best membranes forMEA construction and testing
E.K. Pefkianakis, V. Deimede, M.K. Daletou, N. Gourdoupi, J.K. Kallitsis Macromol. Rapid Commun., 26, 1724, 2005
N.Gourdoupi, A.K. Andreopoulou, V. Deimede, J.K. Kallitsis Chem.Mater., 15, 5044, 2003
O
N N
OR
RO
O Xn
O O SO2
N
N
ON
O SO2
x y
O
N
O X
n
Structural
Characteristics
Aromatic Polyether
High Thermal Stability
High Chemical Stability
Pyridine Polar Group
H+ Acceptor site
Hydrogen Bond site
Route to Design and Synthesis of Novel Polymers(Aromatic Polyethers bearing Polar Groups)
Route to Design and Synthesis of Novel Polymers(Aromatic Polyethers bearing Polar Groups)
Temperature: 180 oC
Ambient pressure
Feed : H2/air
Anode: 1.2
Cathode: 2.0
0,0 0,2 0,4 0,6 0,8 1,0
100
200
300
400
500
600
700
800
900
1000
Advent TPS-2
1st generation product
2nd generation product
3nd generation productPotential, mV
Current Density, mA/cm2
110%6837803rd generation
55%6315902nd generation
-5943751st generation
V (mV) at 0.2 A/cm2
I (mA/cm2)at 0.5V
Increase in performance
PerformanceAdvent TPS-2
Membrane and MEA interface optimization-Advent TPS-2
Membrane and MEA interface optimization-Advent TPS-2
Linear aromatic polyethers containing side crosslinkable units
Linear aromatic polyethers containing side crosslinkable units
Copolymers with free carboxylic side groups
Copolymer ACopolymer A
NHO OH F S
O
O
F
O O OS
O
O
S
O
O
+ +
x 1-x
OHHO
COOH
N
COOH
O
+ K2CO3 + DMF + Tol
CopolymerCopolymer x x -- yy HH--NMRNMR Film IntegrityFilm Integrity
1 MX145 60-40 60-40 ���� ���� ����
2 MX149 65-35 55-45 ���� ���� ����
3 MX150 75-25 46-54 ����
4 MX151 80-20 70-30 ����
5 MX152 60-40 53-47 ���� ����
6 MX153 75-25 71-29 ���� ���� ����
7 MX154 85-15 59-41 ����
8 MX157 60-40 54-46 ���� ���� ����
9 MX159 80-20 71-29 ����
10 MX160 85-15 70-30 ����
TGA thermographs in nitrogen atmosphere of the copolymers MX145(60-40)
before (----) and after Fenton Test(----)
N
* OO2S O O
COOH
O2S
60 40
Temperature dependence of the storage (E’) and loss (E”)modulus for the copolymers MX145(60-40) before (----)
and after Fenton Test(----)
100 125 150 175 200 225 250
0
500
1000
1500
2000
2500
3000
Temperature(oC)
E'(MPa)
0
100
200
300
400
500
600
700
MX145(Before Fenton)
MX145(After Fenton)
E"(MPa)
0 200 400 600 800
50
60
70
80
90
100
Weight(wt%
)
Temperature(oC)
Before Fenton Test
After fenton Test
TGATGA DMADMA
Thermal Properties of the Copolymers with free carboxylic side groups
Thermal Properties of the Copolymers with free carboxylic side groups
3%3,5%100%24
0%0%100%5
0%0%100%1
MX197 crossMX196 crossMX145
(COOH)Time (h)
Soluble fraction
MX145(COOH)
MX197 crosslinked
MX196 crosslinked
Crosslinking of Carboxyl bearing polymersCrosslinking of Carboxyl bearing polymers
50 100 150 200 250 300
0
200
400
600
800
1000
1200
1400
1600
1800
2000
2200
2400
2600
E''(MPa)
copolymer(COOH)
copolymer crosslinked in 2 steps
copolymer Direct crosslinking
Temperature(oC)
E'(MPa)
0
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
1400
1500
Properties of the
Crosslinked Polymers
DMADMA
226+2.9142500489506750/50B11
230+2.4156000650008080/20B10
228+2.792100338007360/40B9
225+2.6641502390083.470/30B8
---3.1788002540088.780/20B7
198+234550167806860/40B6
--2.7556702030082.580/20B5
204+1.944400220007770/30B4
198+2.0461102200066.660/40B3
215+2.333800144007060/40B2
--2.8280001000079.580/20B1
TgFILMIMwMncx/ybx/yaCODE
Linear aromatic polyethers containing side crosslinkable units
Linear aromatic polyethers containing side crosslinkable units
a Compositions as determined by the monomers’ feed ratiob Compositions as determined by the 1 H NMRC GPC in CHCl3
Crosslinking of side double bondsCrosslinking of side double bonds
-82320.3VIIIB8
B10
B9
B9
B4
B4
B3
B2
B1
Copolymer
-1.52320.5X
-52900.3IXa
-1.72900.5IX
-92500.3IVa
-14,52140.93IV
-182220.93III
-2,72800.3II
-9,7-0.93I
Solubility in DMAc
Tgeqdb/
eqCrosslinker
CODE OF CROSSLINKED
POLYMER
C For 5 hours at 55 oC
0 50 100 150 200 250 300 350 400
0
200
400
600
800
1000
1200
1400
E'(MPa) E
''(MPa)
T (oC)
B9
IXa
IX
0
20
40
60
80
100
120
140
160
180
0 50 100 150 200 250 300 350
0
500
1000
1500
2000
2500 B8
VIII
E''(M
Pa)E
'(MPa)
T (oC)
0
50
100
150
200
250
300
0 50 100 150 200 250
0
200
400
600
800
1000
1200
1400
1600
1800
2000
2200
2400
B3
III
T (oC)
E'(MPa)
0
50
100
150
200
250
300
E''(M
Pa)
0 50 100 150 200 250 300
0
200
400
600
800
1000
1200
1400
1600
1800
2000
B2
II
E'(MPa)
E''(M
Pa)
T (oC)
0
20
40
60
80
100
120
140
160
180
200
Crosslinking of side double bondsCrosslinking of side double bonds
0.0 0.2 0.4 0.6 0.8
200
250
300
350
400
450
500
550
600
650
700
750
800
850
900
180 0C
200 0C
210 0C
220 0C
230 0C
i , A/cm2
voltage , mV
normal flows (H2/O
2(air) = 1.2/2.0)
0.0 0.2 0.4 0.6 0.8
0
100
200
300
400
500
600
700
800
900
1000
H2/Air 1.2/2.0
180 oC
230 oC
V, mV
I, A/cm2
Increase of the Operation TemperatureIncrease of the Operation Temperature
0.0 0.2 0.4 0.6 0.8
0
100
200
300
400
500
600
700
800
900
1000
voltage , mV
i , A/cm2
180 0C
200 0C
220 0C
180 190 200 210 2200.100
0.101
0.102
0.103
0.104
0.105
0.106
0.107
0.108
0.109
Ionic conductivity
σ (
S/c
m)
T(OC)
0.0 0.2 0.4 0.6 0.8
300
400
500
600
700
800
900
1000
stability of MEA 1 at 200 0C
voltage , mV
i , A/cm2
0 hours
after 24 hours
after 30 hours
after 48 hours
Increase of the Operation Temperature of the MEAsbased on Crosslinked Copolymers B
Increase of the Operation Temperature of the MEAsbased on Crosslinked Copolymers B
I-V Curves of MEA 1II--V Curves of MEA 1V Curves of MEA 1
Hydrogen / Air
DL of MEA 1 = 250%
STABILITY of MEA 1 at 200STABILITY of MEA 1 at 200ooCC
0.1080.1050.101Conductivity
(S/cm)
0.670.60.53Current at 500
mV
670653634Voltage (mV)
at 0.2A/cm2
220200180Temperature
(oC)
Increase of the Operation Temperature of the MEAsbased on Crosslinked Copolymers B
Increase of the Operation Temperature of the MEAsbased on Crosslinked Copolymers B
0.0 0.2 0.4 0.6 0.8
0
100
200
300
400
500
600
700
800
900
1000
200 0C
voltage , mV
i , A/cm2
0 h
24 h
48 h
0.0 0.2 0.4 0.6 0.8
0
100
200
300
400
500
600
700
800
900
1000
voltage , mV
i , A/cm2
180 0C
200 0C
220 0C
180 190 200 210 2200.088
0.090
0.092
0.094
0.096
0.098
0.100
Ionic Conductivity
T(OC)
σ (
S/c
m)
I-V Curves of MEA 2II--V Curves of MEA 2V Curves of MEA 2
Hydrogen / Air
DL of MEA 2 = 195%
STABILITY of MEA 2 at 200STABILITY of MEA 2 at 200ooCC
0.0970.0930.089Conductivity
(S/cm)
>0.80.80.7Current at 500
mV
700687670Voltage (mV)
at 0.2A/cm2
220200180Temperature
(oC)
0 50 100 150 200 250 300
300
400
500
600
700
T = 200oC
Feed = H2/synthetic air
+ 1 A (0.2 A/cm2)
5x5 single cell
(bipolar plates by Nedstack)
Advent TPS (210 µm thickness)
Voltage, mV
Time, h
Increase of the Operation TemperatureIncrease of the Operation Temperature
180 200 220 240 260 280 300
0
20
40
60
80
100
MeOH conversion, %
T, oC
CuMn-ox
180 200 220 240 260 280 300
0
2
4
6
8
10
12
CuMn-red
CO selectivity, % open symbols: 300
oC to RT
solid symbols: RT to 300oC
180 200 220 240 260 280 300
0
20
40
60
80
100
T, oC
CuMn-ox-P150
180 200 220 240 260 280 300
0
2
4
6
8
10
12
open symbols: 300oC to RT
solid symbols: RT to 300oC
CuMn-red-P150
180 200 220 240 260 280 300
0
20
40
60
80
100
T, oC
CuMn-ox-P200
180 200 220 240 260 280 300
0
2
4
6
8
10
12
open symbols: 300oC to RT
solid symbols: RT to 300oC
CuMn-red-P200
�The catalytic activity of oxidized samples is higher when the reaction T goes from higher to
lower values
� The exposure T to H3PO4 doesn’t affect significantly the samples activity
WP3: Reforming catalysts: synthesis and screening
First results on CuMnOx catalysts
WP3: Reforming catalysts: synthesis and screening
First results on CuMnOx catalysts
180 200 220 240 260 280 300
0
20
40
60
80
100
MeOH conversion, %
T, oC
CuMn-ox
180 200 220 240 260 280 300
0
2
4
6
8
10
12
CuMn-ox-P200
CuMn-ox-P150
CO selectivity, %
open symbols: 300oC to RT
solid symbols: RT to 300oC
180 200 220 240 260 280 300
0
20
40
60
80
100
MeOH conversion, %
T, oC
180 200 220 240 260 280 300
0
2
4
6
8
10
12
CuMn-red-P200
CuMn-red-P150
CuMn-red
CO selectivity, %
open symbols: 300oC to RT
solid symbols: RT to 300oC
� In oxidized samples, the exposure to H3PO4 has no negative effect
� In reduced samples, H3PO4 causes deactivation
First results on CuMnOx catalystsFirst results on CuMnOx catalysts
Schematic of the proposed fuel cell stack assemblySchematic of the proposed fuel cell stack assembly
Institut für Mikrotechnik Mainz GmbH
Advanced Energy Technologies
Nedstack Fuel Cell Technology BV
Project deliverablesProject deliverables
D1.1 Management. Procedures preparation, implementation and proposal
improvement
D1.2 Financial, technical, progress, management, mid-term reports
D2.1 Synthesis of new generation membranes based on Advent polymer
D2.2 Characterization of new generation membranes
D3.1 Methanol/ Ethanol reforming catalysts
D3.2 Thorough characterization of structural, redox and adsorptive properties
of the catalysts
D3.3 Report on 500 h long term catalyst testing
D4.1 Preparation of reforming structured catalysts according to C1 configuration
D4.2 Preparation of an electrode with the reforming catalyst integrated in the hydrophobic layer (C2 configuration)
D4.3 Preparation of an electrode with fully mixed reforming catalyst/electrocatalyst (C3 configuration)
D5.1 Electrochemical testing of membranes
D5.2 Electrochemical testing of new electroreforming anode catalysts
D5.3 Understanding of electrochemical interface properties and electrocatalyticmechanism.
D6.1 Construction of bipolar plates which can operate at 190-200°C
D6.2 Single cell long term testing of most promising materials prepared in WP1, WP2 and WP3
D6.3 Post mortem characterization of electrocatalysts, catalysts, membranes and bipolar plates
Project deliverablesProject deliverables
D7.1 Construction of 100W stack, BOP components and control system
D7.3 System integration and 500 hrs test
D7.4 Report on system control strategy
D8.1 Internal dissemination and knowledge management through a secure
access site
D8.2 Web site dedicated to the scientific community
D8.3 Public Dissemination (papers in specialized and non specialized
press, technology transfer brokerage events)
D8.4 Plan for the Use and Dissemination of the foreground
Project deliverablesProject deliverables
� ADVENT TECHNOLOGIES develops new materials and systems for
renewable energy technologies, such as high temperature PEM fuel cells
and hydrogen clean up.
� Advent is primarily focused on high temperature PEM fuel cell membranes
and components.
� Advent also participates in projects for the development of flexible organic
photovoltaics (OPV’s)
� The Company is currently headquartered in Athens, Greece with research
and pilot manufacturing facilities in Patras, Greece.
OverviewOverview
Advent Technologies SA
Polymer Chemistry
Laboratory
University of Patras
Electrocatalysis Laboratory
FORTH-ICEHT
European and Greek Grants
JOULE III 1998-2001
APOLLON 2002-2005
PYTHAGORAS 2004-2006
PEMHYGEN 2003-2007
PROMETHEAS 2002-2006
APOLLON-B 2006-2009
Development of revolutionary technology
in the area of High Temperature MEAs
Incorporation of
ADVENT TECHNOLOGIES SA (2005)
and establishment of the
ADVENT TECHNOLOGIES NORTH AMERICA INC (2006)
Funding from PRAXE and institutional and
industrial investors from
Greece and abroad (e.g.
Piraeus Bank Capital
Management VC, Sunlight
Systems, Velti, Eltpa-
Provoli, Dolphin Capital,
ILPRA etc.)
HistoryHistory
From basic research to a productFrom basic research to a product