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Dept. of Chemical Eng. Yonsei Univ. Prof. Y.G. Shul, H.S. Kim
Fuel Cell Applications Heteropolyacid(HPA)-SiO2 nanoparticles for high temperature operation of a direct methanol fuel cell Preparation and characterization of new carbon for fuel cell application Pulse Electrodeposition for Preparing PEM Fuel Cell Electrode Investigation of alloy catalyst for accelerating hydrogen release from NaBH4
In this study
Nano scale
SiO2
Heteropoly acid
Characterization :
TEM, Solid state NMR, TMP adsorption, N2 adsorption, FT-IR
Heteropolyacid-SiO2 nanoparticles
100 nm
100nm
R= [H2O]/[AOT] X=[Heteropolyacid]
31P
MAS NMR
H3PW12O406H2O
Dehydration of heteropolyacid
-15.6ppm
Dehydration
Heteropolyacid
-15.1ppm
500nm
[ PW12O40 ]3
H+ OH Si
-20
-15.0ppm
Bulk
H+ OH Si
H+ OH Si
-10
-12
-14
-16
-18
Referenced from - M.Misono et al., J.Phys.Chem.B., 104 (2000) 8108 - F.Lefebvre et al., J.Chem.Soc.Chem.Commun, (1992) 756
13C
CP MAS NMR
27.9 ppm
(a)
18.2 ppm
11.4 ppm
54.0 ppm
(b)
60
50
40
30
20
10
CP MAS NMR spectra (a) thiol- and (b) sulfonic-functionalized heteropolyacid-SiO2 nanoparticle.
13C
H2O HPA
+ SO3 Na
O
Sol-gel process
Si(OR)4 + 4H2O Si(OH)4 + 4ROH
Cyclohexane TEOS
600
0.05
0.9 0.8
Pore fraction
Pore ratio
R < 1nm
500
0.04
DV/DR (cm3/g)
400
R > 3nm
1 2 3
300
Bulk
500nm 100nm
0.02
200
Surface area
100
0.01
0.00
HPA
Bulk
500nm
100nm
20
40
60
80
Application to DMFC
Pressure gauge
2way valve Needle valve 6 way valve Methanol 2M solution. Fuel heater
O2 Tank
G.C
(a)
6.510-5 S/cm
(b)
80
14
12 10 8 6 4 2
Heteropolyacid-SiO2 nanoparticle
60
Z''(ohm)
Heteropolyacid-SiO2 nanoparticle
40
20
Z'(ohm)
Complex impedance response(a) and methanol crossover rate(b) of the sulfonated polysulfone and sulfonated polysulfone / heteropolyacid SiO2 nanoparticle composite membrane.
10
100
(a)
Crossover rate (mol/cm2*min)
8
80
(b)
60
40
0 0 5 10 15 20 25
Temperature (oC)
Proton conductivity(a) and methanol crossover rate(b) of the sulfonated polysulfone and sulfonated polysulfone / heteropolyacid SiO2 nanoparticle composite membrane.
H2O
100
H3O+
0.8 80 oC 160 oC 200 oC 60 50
Transmittance (%)
60
40
0.4
30
40
20 0.2
20
10
0 4000
0.0
3500
3000
2500
2000
-1
1500
1000
Wavenumber (cm )
0.6
DMFC
Great potentiality for DMFC support Johnson Mattheyat 0.4V, 135 mA/cm2 (80oC) Improvement in liquid mass transfer for catalyst3nm PtSn/XC-72 0.4V, 80 mA/cm2 Similar reference with Pt-Ir on carbon paper Mg: anode Microfiber carbon :cathode cathode side: 0.20M H2O2 Great potentiality for DMFC support material
DEFC
Carbon fiber
1.5V, 300mA/cm2
DMFC
I-V curve for electrodes with commercial Pt/C and Pt/C+ Pt/ACF (900)
1.1 1.0 0.9 0.8 Commercial Pt/C Commertial Pt/C (70%)+ Pt/ACF(30%.400oC) Commertial Pt/C (70%)+ Pt/ACF(30%.900oC)
Voltage ( V )
0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4
Performance increasing
Cell Temp. : 80, Humidify condition : RH% 100 anode and cathode, Flow rate: Stoichiometry 1.5(Anode):2.0(Cathode)
0.08
0.25
0.20
-Z'' / O hm
-Z'' / O hm
0.08 0.10 0.12 0.14 0.16 0.18 0.20 0.22 0.24 0.26
0.06
0.15
0.04
0.10
0.02
0.05
0.00 0.06
Z' / Ohm
Z' / Ohm
Specific surface area and average pore diameter of the CNF treated by KOH
Surf. area (m2 /g) 107.60 444.18 509.95 645.53 460.10 375.52 341.87 303.54 Avg. Pore diameter ( ) 62.21 46.07 48.80 48.0 44.33 54.41 62.37 58.01
CNF
Activation condition No activation 750-1h 800-1h 900-1h 900-2h Modified method 900-3h 950-1h
5H
900-2h
MDF(900-2h)
A/(900-2h) (a)
B/(900-2h) (b)
B/MDF(900-2h) (c)
50 nm
50 nm
50 nm
H2
C2H4
a c b a, b
Reduction in He/H2
inactive
P t/A C F -C N F s P t/C ( C o m m e r c ia l)
Pt(2 0 0)
Intensity(a.u.)
Pt(2 2 0)
30
40
50
60
70
80
2 th e ta
0.9
0.8
Voltage(V)
0.7
0.6
0.5
Current density(A/cm 2 )
Carbon clothe
Back-Scattered Electron Image and Pt Line Scan of The Cross Section of MEA using EPMA
membrane E-TEK Pt/C layer E-TEK GDL
200.0
PC layer GDL
Pt
100.0
ESEM Image and Pt Concentration Profile of the Cross Section of MEA Using EDX Spot Analysis
80
E-TEK electrode
60
PC deposition electrode
Pt wt%
Membrane
40
0 0 2 4 6 8 10 12 14
0.9
0.8
Potential (V)
0.7
0.6
0.5
0.4
2.1
2.4
2.7
H2
H2 Coolant
NaBH4 Reduction
Hydrolysis
Coolant
30 25 20 15 10 5 0
-1 -1 ) (Lmin g
30 25
Ru
Ru
Co
Ni
Co
Fe
Hydrogen release rate of (a) Ru-Co-Ni, (b) Ru-Co-Fe from 10 wt% NaBH4 solution with 4 wt% NaOH (Temperature fixed to 25C)
XRD Patterns
CoFe2O4 RuCoFe
(c)
(b)
(a)
Co and Fe were not reduced completely when NaBH4 only was used for reduction. After the additional reduction by using hydrogen, CoFe alloy were shown
70
Intensity
30
40
50
60
2 theta
XRD Patterns of (a) Ru/ACF; (b) NaBH4-reduced Ru0.6Co0.2Fe0.2/ACF; (c) NaBH4 and H2-reduced Ru0.6Co0.2Fe0.2/ACF catalyst
RuCoFe/ACF nanocatalyst
100
3.5
80 60 40 20 0 10 15 20 25 T / oC 30 35
3.0 2.5 ln k
(b) (a)
(e)
40
3.20
3.25
3.30
3.35 1000 / T
3.40
3.45
3.50
catalyst (a ) (b ) (c) (d ) (e ) 10 wt% Ru/ACF 16 wt% Ru0.6Co0.2Fe0.2/ACF 16 wt% Ru0.6Co0.2Fe0.2/ACF 13 wt% Ru0.75Co0.25/ACF 16 wt% Ru0.6Co0.2Fe0.2/ACF
Conclusions
Nano materials may lead to drastic improvement in fuel cell application 1)Nanohybride electrolyte (HPA-SiO2+Nafion) was effective for the high temperature operating of DMFC 2)New nano carbons are promising to enhance the catalytic activity in fuel cell 3) Nano alloy will be effective to release control of the H2 from chemical hydride (NaBH4, NH3BH3) 4) Electrodeposition is effective to reduce the amount of Pt loading
Acknowledgement
Backup slides
Impedance spectra
0.08
Membrane resistance Interfacial resistance (Mixture ratio 20%Pt/C:20%Pt/ACF-CNFs) Only 20% Pt/C
0.063
-Z''/Ohm
0.06
0.04
0.02
3:7
Z'/Ohm
Cyclic voltammogram
0 .4
0 .2
0 .0
-0 .2
i/A
-0 .4 -0 .6 P t/C P t/A C F -C N T s 3 0 % -0 .8 -1 .0 -0 .2 0 .0 0 .2 0 .4 0 .6 0 .8 1 .0 1 .2
E /V
Material Cost
0.2 g (Pt loading)/peak kW Non-precious catalyst (Pt-free)
Durability
40,000 hours operation with <10% performance degradation in stationary applications.
bs 2 J = K1 exp zekT
= + log i
Pulse electrodeposition Off time Concentration of electrolyte is recovered Electrodeposition at high current density
Current density 1 ip 2
ia time
K1 - rate constant S - surface area occupied by one atom on the surface of the nucleus e - the charge of the electron z - the electronic charge of the ion k - the Boltzmann constant T - the temperature b=P2/4S, where P is the perimeter and S is the surface area i current applied , Tafel constants Overpotential 1: on time 2: off time Ip: peak current density Ia: average current density Duty cycle: 1/
t1
t2
t3
t4
t5
Comparison of the Limiting Current Density between Pulse and Direct Electrodeposition
diffusion model by H. Y. Cheh,
(idc )l
0.4 0.6 0.8 1.0
(i )
p l
1 = 0.2
( idc )l
(i )
p l
exp ( 2 j 1) a 1) ( 8 1 1 ( 2 j 1) ( exp 2 j 1) a 1) (
2 2 2 j =1 2 2
aa
a = 2 D / 4 2
(sec 1 )
Pulse
DC
50mA/cm DC 200mA/cm2 PC
0.8
0.7
Potential (V)
0.6
0.5
0.4
0.3
0.2 0.0
Nafion 112 Cell Temperature: 75 oC H2/O2 (flow rate: 1.5/2 stoichiometric) Pressure: 1atm
0.3 0.6 0.9 1.2 1.5
2
1.8
2.1
2.4
The conditions of pulse electrodeposition: 200mA/cm2 of peak current density, 5.2ms on time and 70ms off time. Total charge is fixed at 6C/cm2 on both cases.
SEM Images of Pt Electrodeposited Electrodes by D.C or P.C mode. (Total charge is fixed at 6C/cm2 on both cases)
200mA/cm2 of peak current density, 5.2ms on time and 70ms off time
Effect of the peak current density of pulse electrodeposition on the performance of the PEM fuel cell
1.0 0.9
0.8
0.7
10 mA/cm2 DC 30 mA/cm2 PC 100 mA/cm2 PC 200 mA/cm2 PC 400 mA/cm2 PC 2 600 mA/cm PC
Potential (V)
0.6
0.5
0.4
0.3
0.2 0.0 0.3 0.6 0.9 1.2 1.5 1.8 2.1 2.4 2.7
Cyclic Voltammograms of the Electrodes Prepared at Different Peak Current Densities in Pulse Electrodeposition
1.0
0.5
0.0
-0.5
600mA/cm2 30mA/cm2
-1.0
200mA/cm2
400mA/cm2 100mA/cm2
-1.5 -0.8
-0.6
-0.4
-0.2
0.0
0.2
0.4
0.6
0.8
0.9
0.8
0.7
Potential (V)
0.6
0.5
0.4
0.3
2.1
2.4
2.7
3.0
Comparison of Pt line scan image in the cross section of the MEA (A) 8C/cm2 and (B) 20C/cm2
Cps
300
Cps
300
(A)
(B)
0 0 40
0 0 40
Microns (m)
Microns (m)