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Development of high temperature PEM fuel cells. Simplification and CO tolerancemapping
Jensen, Jens Oluf; Fernandez, Santiago Martin; Vassiliev, Anton; Cleemann, Lars Nilausen; Li, Qingfeng
Publication date:2015
Document VersionPublisher's PDF, also known as Version of record
Link back to DTU Orbit
Citation (APA):Jensen, J. O. (Author), Fernandez, S. M. (Author), Vassiliev, A. (Author), Cleemann, L. N. (Author), & Li, Q.(Author). (2015). Development of high temperature PEM fuel cells. Simplification and CO tolerance mapping.Sound/Visual production (digital)
DTU Energy Technical University of Denmark
Development of
high temperature PEM fuel cells.
Simplification and CO tolerance mapping Jens Oluf Jensen, Santiago Martin, Anton Vassiliev, Lars N. Cleemann and Qingfeng Li Proton Conductors Department of Energy Conversion and Storage Kemitorvet 207 Technical University of Denmark DK-2800 Lyngby Denmark [email protected]
J.O. Jensen – at "Neptune’s Hydrogen and Fuel Cells", Naples, Dec. 15, 2015
DTU Energy Technical University of Denmark
J.O. Jensen – at "Neptune’s Hydrogen and Fuel Cells", Naples, Dec. 15, 2015
Outline
• The choice of fuel
• CO effect on the PEM fuel cell
• Binderless electrodes
• Lowering the platinum loading
DTU Energy Technical University of Denmark
J.O. Jensen – at "Neptune’s Hydrogen and Fuel Cells", Naples, Dec. 15, 2015
Fueling of fuel cells
Type I Hydrogen
Type II Methanol Dimethyl ether
Type III Natural gas Gasoline/diesel LPG Ethanol
LT PEMFC
Simple reformer
Complex reformer
Purification
HT-PEMFC
Fuel Reforming Purification Fuel cell
DTU Energy Technical University of Denmark
J.O. Jensen – at "Neptune’s Hydrogen and Fuel Cells", Naples, Dec. 15, 2015
Fueling of fuel cells
Type I Hydrogen
Type II Methanol
Dimethyl ether
Type III Natural gas
Gasoline/diesel LPG
Ethanol
Hydrogen Methanol HC
Fuel efficency Systme simplicity Availability Ease of storage
DTU Energy Technical University of Denmark
J.O. Jensen – at "Neptune’s Hydrogen and Fuel Cells", Naples, Dec. 15, 2015
FC temperatures
RT 200ºC 600ºC 1000ºC
MCFC (O2- as CO32-)
SOFC (O2-)
PEMFC (H+)
AFC (H+ via OH-)
PAFC (H+)
100ºC
High temperature fuel cells
Intermediate temperature
fuel cells ?
Low temperature fuel cells
DTU Energy Technical University of Denmark
J.O. Jensen – at "Neptune’s Hydrogen and Fuel Cells", Naples, Dec. 15, 2015
Results with PBI membranes
N
N
N
Nn
HH
Poly (2,2´-m-(phenylene)-5,5´-bibenzimidazole)
Well-known temperature resistant polymer Tg = ~430ºC
When doped with phosphoric acid:
Proton conductor
Wainright and Savinell. J. Electrochem. Soc. 142 (1995) L121
Polybenzimidazole
DTU Energy Technical University of Denmark
J.O. Jensen – at "Neptune’s Hydrogen and Fuel Cells", Naples, Dec. 15, 2015
Reformer / Reformer Brændselscelle / Fuel cell
El Nat. Gas, Methanol
H2 CO2 CO CO-oprensning
til 0,001 % CO clean-up to 0,001 %
H2 CO2
Varme/heat
Luft ind Air in
Luft ud Air out
Befugtning af luften Humidification of the air
DTU Energy Technical University of Denmark
J.O. Jensen – at "Neptune’s Hydrogen and Fuel Cells", Naples, Dec. 15, 2015
Luft ind Air in
Luft ud Air out
Befugtning af luften Humidification of the air
H2 CO2
H2 CO2 CO CO-oprensning
til 0,001 % CO clean-up to 0,001 %
Reformer / Reformer Brændselscelle / Fuel cell
El Nat. Gas, Methanol
Varme/heat
DTU Energy Technical University of Denmark
Integration with methanol reformer
J.O. Jensen – at "Neptune’s Hydrogen and Fuel Cells", Naples, Dec. 15, 2015
Li Qingfeng et al. Electrochemical and Solid-State Letters, 5 (6) A125-A128 (2002)
Oxygen MeOH +H2O
Pump
Ref
orm
er
200º
C
Condenser
Fuel cell 200ºC
DTU Energy Technical University of Denmark
J.O. Jensen – at "Neptune’s Hydrogen and Fuel Cells", Naples, Dec. 15, 2015
CO tolerance
BA
SF,
Cel
tec®
P11
00W
pro
spec
t
DTU Energy Technical University of Denmark
J.O. Jensen – at "Neptune’s Hydrogen and Fuel Cells", Naples, Dec. 15, 2015
Response to diluted hydrogen
0
50
100
150
200
250
300
350
400
0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1
0 500 1000 1500Po
wer
den
sity
/ m
W c
m-2
Volta
ge /
V
Current density / mA cm-2
0% CO0.7% CO2.5% CO
Model composition: CO: 0.7%; H2: 34.8%; N2: 64.5% CO: 1.7%; H2: 33.9%; N2: 64.4%
0
50
100
150
200
250
300
350
400
0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1
0 500 1000 1500
Pow
er d
ensi
ty /
mW
cm
-2
Volta
ge /
V
Current density / mA cm-2
0% CO0.7% CO1.7% CO
λH2 = 1.2 (0.35 mgPt cm-2) λair = 2.0 (0.83 mgPt cm-2)
DTU Energy Technical University of Denmark
J.O. Jensen – at "Neptune’s Hydrogen and Fuel Cells", Naples, Dec. 15, 2015
Dilution of hydrogen with CO λ(air): 2, λ(H2): 1.5 Cathode: 1.3 mgPt cm-2 Anode: 1.3 mgPt cm-2.
100% H2
1%CO;99%H2
1%CO;20%H2
(160ºC)
100% H2
1%CO;99%H2 1%CO;20%H2
DTU Energy Technical University of Denmark
J.O. Jensen – at "Neptune’s Hydrogen and Fuel Cells", Naples, Dec. 15, 2015
High surface adsorption, Langmuir Equilibrium:
or: θθ NkPNk da =− )1(
KPKP
Pkk
Pkk
d
a
d
a
+=
+=
11θ
K = K(T)
N: no. of sites θ: surface fraction occupied P: pressure t: time ka, kd: rate constants for adsorption and desorption
kd
ka
Catalyst
Cov
erag
e
Activity (pressure)
Higher reactant partial pressure
⇓ higher reaction rate
(current) At any given polarization
DTU Energy Technical University of Denmark
J.O. Jensen – at "Neptune’s Hydrogen and Fuel Cells", Naples, Dec. 15, 2015
Competition with CO
H2 coverage CO coverage
Langmuir basis for H2 Langmuir basis for CO
cba
DTU Energy Technical University of Denmark
0 200 400 600 800 1000 1200 1400 16000.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0 Pure H2 at 1 h 0.2 ppm H2S at 2 h 0.5 ppm H2S at 4 h 1 ppm H2S at 6 h 2 ppm H2S at 7 h 5 ppm H2S at 10 h 10 ppm H2S at 12 h 20 ppm H2S at 13 h 50 ppm H2S at 14 h Pure H2 at 22 h
Cel
l pot
entia
l (V
)
Current density (mA/cm²)
160 °C, 1 mg/cm² Pt/C, λH2=1.2, λair=2
J.O. Jensen – at "Neptune’s Hydrogen and Fuel Cells", Naples, Dec. 15, 2015
DTU Energy Technical University of Denmark
0 200 400 600 800 1000 1200 1400 16000.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0 Day 2, pure H2
Day 2 + 2 hours, 2 ppm H2S Day 2 + 7 hours, 2 ppm H2S Day 3, 2 ppm H2S Day 4, 2 ppm H2S Day 5, 2 ppm H2S Day 5 + 2 hours, pure H2
Day 6, pure H2, stable
Cel
l pot
entia
l (V
)
Current density (mA/cm²)
160 °C, 1 mg/cm² Pt/C, λH2=1.2, λair=2
J.O. Jensen – at "Neptune’s Hydrogen and Fuel Cells", Naples, Dec. 15, 2015
DTU Energy Technical University of Denmark
J.O. Jensen – at "Neptune’s Hydrogen and Fuel Cells", Naples, Dec. 15, 2015
Reduction of binder
Experiments say: Less binder (PBI) gives better performance. What is the optimum/minimum?
What happens if we go to the extreme and make electrode completely without the binder? 1. Nothing. The binder is not needed 2. The catalyst layer falls off too easily 3. The proton transport is mostly blocked 4. Reduction to a certain level improved performance and then
it breaks down
DTU Energy Technical University of Denmark
J.O. Jensen – at "Neptune’s Hydrogen and Fuel Cells", Naples, Dec. 15, 2015
Single cell dev., binderless electrodes
Ultrasonic stirring
(1 hour)
Ultrasonic spraying d=13cm
Flow rate=0.25ml/min Catalytic suspension
Catalytic deposit
New ink
Pt/C Ethanol
Ultrasonic stirring
(24 hours)
Catalytic suspension
Catalytic deposit
Standard ink
Pt/C H3PO4 PBI
Formic acid
Ultrasonic spraying d=13cm
Flow rate=0.25ml/min
DTU Energy Technical University of Denmark
J.O. Jensen – at "Neptune’s Hydrogen and Fuel Cells", Naples, Dec. 15, 2015
Binderless electrodes
S. M
artin
, Q. L
i, T.
Ste
enbe
rg, J
.O. J
ense
n.
J. P
ower
Sou
rces
272
(201
4) 5
59-5
66
H2/Air, 160°C
DTU Energy Technical University of Denmark
J.O. Jensen – at "Neptune’s Hydrogen and Fuel Cells", Naples, Dec. 15, 2015
Binderless electrodes
S. M
artin
, Q. L
i, T.
Ste
enbe
rg, J
.O. J
ense
n.
J. P
ower
Sou
rces
272
(201
4) 5
59-5
66
H2/Air, 160°C
DTU Energy Technical University of Denmark
J.O. Jensen – at "Neptune’s Hydrogen and Fuel Cells", Naples, Dec. 15, 2015
Reducing Pt loading on anode
S. M
artin
, Q. L
i, T.
Ste
enbe
rg, J
.O. J
ense
n.
J. P
ower
Sou
rces
272
(201
4) 5
59-5
66
DTU Energy Technical University of Denmark
J.O. Jensen – at "Neptune’s Hydrogen and Fuel Cells", Naples, Dec. 15, 2015
Reducing Pt loading on cathode
S. M
artin
, Q. L
i, T.
Ste
enbe
rg, J
.O. J
ense
n.
J. P
ower
Sou
rces
272
(201
4) 5
59-5
66
DTU Energy Technical University of Denmark
J.O. Jensen – at "Neptune’s Hydrogen and Fuel Cells", Naples, Dec. 15, 2015
Reducing Pt loading to 0.1 mgPt /cm2 (each)
S. M
artin
, Q. L
i, J.
O. J
ense
n.
J. P
ower
Sou
rces
293
(201
5) 5
1-56
No markers: SOA, 0.6/0.6 mg Markers: 0.1/0.1 mg
DTU Energy Technical University of Denmark
J.O. Jensen – at "Neptune’s Hydrogen and Fuel Cells", Naples, Dec. 15, 2015
Reducing Pt loading to 0.1 mgPt /cm2
S. M
artin
, Q. L
i, J.
O. J
ense
n.
J. P
ower
Sou
rces
293
(201
5) 5
1-56
DTU Energy Technical University of Denmark
J.O. Jensen – at "Neptune’s Hydrogen and Fuel Cells", Naples, Dec. 15, 2015
A closer look a the catalyst materials (JM) Pt on carbon / wt.% 10 20 40 60
Pt loading cathode/anode / mg cm-2 0.098/0.094 0.098/0.094 0.098/0.096 0.098/0.098
Peak power densitya / mW cm-2 321(482) 301 268 215
Pt utilizationa / kWgPt-1
overall cathodic
1.67(2.51) 3.27(4.92)
1.57 3.08
1.38 2.73
1.10 2.19
Voltage at 200 mA cm-2,a / V 0.557(0.618) 0.544 0.513 0.489
Catalyst layer thickness / μm ~ 18 ~ 8 ~ 3.5 ~ 2.5
Pt XRD crystallite sizeb / nm 2.5 2.7 3.3 3.2
DTU Energy Technical University of Denmark
J.O. Jensen – at "Neptune’s Hydrogen and Fuel Cells", Naples, Dec. 15, 2015
Partial flooding?
DTU Energy Technical University of Denmark
J.O. Jensen – at "Neptune’s Hydrogen and Fuel Cells", Naples, Dec. 15, 2015
Acknowledgement
" Development of Auxiliary Power Unit for Recreational
yachts “ (PURE)
Grant agreement no: 303457
Seventh Framework Programme
Book, Springer 2015