Nano Material Applications in Fuel Cell

Dept. of Chemical Eng. Yonsei Univ. Prof. Y.G. Shul, H.S. Kim

Nano Materials in Fuel Cell

Hydrogen Release Catalyst

Novel Anode Catalyst Organic-Inorganic Membrane

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

Preparation nanohybride particle (HPA/SiO2) By micro emulsion technique

. .. . .. . .. . . . .... .. . . . .. ..... .... .. . . .. . . . . . . ... . .. . . . .. . . . . . . . . . . . . . ... . . . .... . . .. ...... . . . ... . .... . ... .. . . . . .. . . . . . . . . . . . . . ... .. .. . . . . . .. . .. . . .. . . .

Nano scale

SiO2

Heteropoly acid
Characterization :
TEM, Solid state NMR, TMP adsorption, N2 adsorption, FT-IR

Heteropolyacid-SiO2 nanoparticles

100 nm

100nm

TEM image of heteropolyacid-SiO2 nanoparticle (R=2, X=30%, 12hr)

TEM image of heteropolyacid-SiO2 nanoparticle (R=2, HPA 30%, 24hr)

R= [H2O]/[AOT] X=[Heteropolyacid]

31P

MAS NMR
H3PW12O406H2O

Dehydration of heteropolyacid
-15.6ppm

Dehydration
Heteropolyacid

Heteropolyacid < nanoparticle < Bulk powder

Trapping of acidic proton to OH group

-15.3ppm
100nm

-15.1ppm

500nm

[ PW12O40 ]3
H+ OH Si
-20

-15.0ppm
Bulk

H+ OH Si

H+ OH Si

-10

-12

-14

-16

-18

Chemical shift (, ppm)

Fig. 31P MAS NMR spectra of heteropolyacid and HPA/SiO2

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

Chemical shift (, ppm)

CP MAS NMR spectra (a) thiol- and (b) sulfonic-functionalized heteropolyacid-SiO2 nanoparticle.

13C

Preparation of inorganic particles in microemulsion

Aerosol-OT
O O O

H2O HPA

+ SO3 Na
O

Sol-gel process
Si(OR)4 + 4H2O Si(OH)4 + 4ROH

Cyclohexane TEOS

Si-OH + HO-Si Si-O-Si + H2O

Surface area vs. nano HPA/SiO2

600

0.05

0.9 0.8

Pore fraction

0.7 0.6 0.5 0.4 0.3 0.2 0.1

Pore ratio
R < 1nm

500

0.04

BET Surface area (m /g)

DV/DR (cm3/g)

400

0.03 100nm HPA/SiO2 500nm HPA/SiO2 Bulk HPA/SiO2

R > 3nm
1 2 3

300

Bulk

500nm 100nm

0.02

200

Surface area
100

0.01

Pore size distribution

0.00

HPA

Bulk

500nm

100nm

20

40

60

80

Pore size (A)

Application to DMFC
Pressure gauge

Cell Fuel pump flowmeter

Heteropolyacid Proton conductivity Silica particle Methanol blocker

2way valve Needle valve 6 way valve Methanol 2M solution. Fuel heater

O2 Tank

G.C

Polysulfone/nanoparticle composite membrane

100
18 16

(a)

1.4 10-3 S/cm

6.510-5 S/cm

(b)

Sulfonated polysulfone membrane Composite membrane

80

14

Methanol crossover rate (mol / cm2 min)

12 10 8 6 4 2

Heteropolyacid-SiO2 nanoparticle

60

Z''(ohm)

Heteropolyacid-SiO2 nanoparticle

40

20

0 45 50 55 60 65 70 75 80 85 90 95 100 105 110

0 20 40 60 80 100 120 140

Z'(ohm)

Cell temperature (oC)

Complex impedance response(a) and methanol crossover rate(b) of the sulfonated polysulfone and sulfonated polysulfone / heteropolyacid SiO2 nanoparticle composite membrane.

Nafion/nanoparticle composite membrane

10

100

(a)
Crossover rate (mol/cm2*min)
8
80

(b)

Nafion membrane Composite membrane

conductivity x10 (S/cm)

A little decrease of proton conductivity

60

40

Reduction of methanol crossover

20

0 0 5 10 15 20 25

0 0 20 40 60 80 100 120 140 160

Content of nanoparticles (%)

Temperature (oC)

Proton conductivity(a) and methanol crossover rate(b) of the sulfonated polysulfone and sulfonated polysulfone / heteropolyacid SiO2 nanoparticle composite membrane.

Nafion-HPA/SiO2 composite membrane

(Nafion / sulfonated heteropolyacid-SiO2 nanoparticle composite membrane)

H2O
100

H3O+
0.8 80 oC 160 oC 200 oC 60 50

80 Heteropolyacid - SiO2 nanoparticle

Transmittance (%)

60

Cell voltage (V)

Sulfonated heteropolyacid - SiO2 nanoparticle

40

0.4

30

40

20 0.2

20

10

0 4000

0.0

0 0 50 100 150 200 250 300

3500

3000

2500

2000
-1

1500

1000

Wavenumber (cm )

Current density (mA/cm2)

FT-IR spectra of sulfonated heteropolyacid-SiO2 nanoparticle

DMFC performance of composite membrane

Improvement of DMFC performance by increasing the cell temperature

Power density (mW/cm )

0.6

Research of carbon material application

Caron structure Pt/CNT FC application PEMFC Performance 0.7V, 0.7 mA/cm2 (50oC) 0.4V, 135 mA/cm2 (65oC) remark high electrocatalytic activity for oxygen reduction 3.60.3nm Reference J.of power sources 139(2005) 73 J.Of power sources 130 (2005) Carbon 42 (2004)

Pt/mesopor ous carbon (SBA-15) PtSn/ MWNT

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

0.4V, 100 mA/cm2

Carbon fiber

Mg-H2O2 Semi-fuel cell DMFC

1.5V, 300mA/cm2

J.Of power sources 96 (2001) 240

Carbon nanocoil Carbon nanohorn

0.4V , 170mA/cm2 (60oC) 0.4V , 130mA/cm2

Angew. Chem 2003,115, 4488 NEC

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

Current density ( A/cm2 )

Commercial Pt/C Current density ( mA/cm2 ) 710

Pt/C+Pt/ACF (400) 807

Pt/C+Pt/ACF (900) 960

Cell Temp. : 80, Humidify condition : RH% 100 anode and cathode, Flow rate: Stoichiometry 1.5(Anode):2.0(Cathode)

Impedance for the electrodes manufactured with Pt/C, Pt/ACF(900) catalysts

0.10
0.30

0.08

Pt/ACF ( 400 C ) Pt/ACF ( 900oC )

0.25

Pt/ACF ( 400oC ) Pt/ACF ( 900oC )

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

0.00 0.0 0.1 0.2 0.3 0.4 0.5

Z' / Ohm

Z' / Ohm

Impedance spectra at 0.7V

Impedance spectra at 0.8V

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

SEM - CNFs named 5H

pristine 800-1h

900-2h

MDF(900-2h)

TEM - 60wt% Pt-Ru/CNF

A/(900-2h) (a)

B/(900-2h) (b)

B/MDF(900-2h) (c)

50 nm

50 nm

50 nm

Growth of nanofiber on ACF

micropores

Surface and Pores of Activated Carbon Fiber

Impregnation of metal salt solution

H2

C2H4

a c b a, b
Reduction in He/H2

Synthesis from C2H4/H2

inactive

Preparation of various carbon substrates

CNF/ACF

Fig. SEM images of carbon nano fibers grown on ACF

Preparation of platinum on ACF-CNFs

TEM Image of Pt/ACF-CNFs

Fig. TEM images of Platinum oncarbon nanofibers grown on ACF

Preparation of platinum on ACF-CNFs

XRD patterns of Pt/ACF-CNFs
Pt(1 1 1)

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

Fig. XRD pattern of Pt/ACF-CNFs

Single cell performance

1.0 Pt/ACF-CNFs 30% Pt/C Pt/ACF-CNFs 20% Pt/ACF-CNFs 100%

0.9

0.8

Voltage(V)

0.7

0.6

0.5

0.4 0.0 0.5 1.0 1.5 2.0 2.5 3.0

Current density(A/cm 2 )

Fig. The performance of Pt/ACF-CNFs used in anode catalyst

Cell Temp. : 80, Humidify condition : RH% 100 anode and cathode, Stoichiometry anode: cathode = 1.5: 2.0 Membrane : nafion 112:, anode : 20%Pt/C, cathode : 20%Pt/C and 20%Pt/ACF-CNFs+20%Pt/C, Back pressure : 1bar

Pulse Electrodeposition for Preparing PEM Fuel Cell Electrode Objectives

Reducing cost of electrode by decreasing Pt loading Decreasing particle size localizing Pt on the surface of electrode in contact with membrane and increasing efficiency of Pt

Advantages of pulse electrodeposition

Low cost Easy of control Versatility

Schematic Diagram of The Electrode Prepared by Pulse Electrodeposition

Catalyst particle

Reactant gas Ion exchange membrane

Carbon clothe

Hydrophobic carbon layer

Hydrophilic carbon layer

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

membrane ETEK layer GDL

100.0

PC deposition Pt/C layer

0.0 0.0 161.0

Distance (m) Microne

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

E-TEK electrode PC deposition electrode

20

0 0 2 4 6 8 10 12 14

Distance from membrane (m)

Comparison of MEA performance between pulse electrodeposited electrode and TKK

1.0
2

0.9

TKK (0.4mg/cm ) 2 PC (0.32mg/cm )

0.8

Potential (V)

0.7

0.6

0.5

0.4

0.3 0.0 0.3 0.6 0.9 1.2 1.5 1.8

2

2.1

2.4

2.7

Current density (A/cm )

High Throughput Screening (HTS) test

Hydrogen release rate of metal catalysts can be measured without catalyst synthesis procedure To apply metal alloy catalyst, amounts of precursor solutions can be mixed to accurate ratios.

Mixed Precursor Solution RuCl3 Co(NO3)2 FeCl2 ..

H2

H2 Coolant

NaBH4 Reduction

Hydrolysis

Coolant

Schematic diagram of simplified HTS test microreactors

Hydrogen release test (Ternary alloy)

30 25 20 15 10 5 0

Rate Generation Hydrogen

-1 -1 ) (Lmin g ation Rate er en G n Hydroge

-1 -1 ) (Lmin g

Ru:Co:Fe = 60:20:20 (wt%)

20 15 10 5 0

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

H2 Release Rate / L min-1gRu-1

80 60 40 20 0 10 15 20 25 T / oC 30 35

(e) (d) (c)

3.0 2.5 ln k

(b) (a)

(e)

2.0 1.5 1.0

(d) (c) (b) (a)

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

Reduction Agent H2 H2 NaBH4 NaBH4 + H2 NaBH4 + H2

hydrogen release rate at 25 C (Lmin-1gRu-1) 14.21 22.63 34.37 37.12 41.73

Activation Energy (kJmol-1) 59.23 47.91 50.54 45.44 44.01

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

0.10 Pt/ACF-CNFs 30% Pt/C Pt/ACF-CNFs 20% Pt/ACF-CNFs 100%

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

0.069 0.175 0.096 0.065

0.04

Only 20% Pt/ACF-CNFs 2:8

0.02

3:7

0.00 0.05 0.10 0.15 0.20 0.25

Z'/Ohm

Fig. Impedance spectra of single cell

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

Fig. Cyclic voltammograms of Pt/ACF-CNFs used oxygen

Technical Barriers of Electrodes for PEM Fuel Cells Electrode performance

400 mA/cm2 at 0.8V with H2/Air and 1atm Novel method of pulse electrodeposition Pt-X alloy

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.

Why Pulse Electrodeposition (Dependence of Nucleation Rate on Overpotential)

Rate of 2D-nucleation * Tafel expression for overpotential

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 )

TEM and SEM image of Pt electrodeposited electrodes

Pulse

DC

Polarization Curves of MEAs Prepared by Direct Current and Pulse Electrodeposition

1.0 0.9

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

Current density (A/cm )

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)

50mA/cm2 of D.C. electrodeposition

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

Current density (A/cm2)

Cyclic Voltammograms of the Electrodes Prepared at Different Peak Current Densities in Pulse Electrodeposition
1.0

0.5

Current density (mA/cm )

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

Potential (V. Hg/Hg2SO4)

Effect of Charge Density on the Performance of PEM Fuel Cell

1.0

0.9

0.8

6C/cm 2 8C/cm 2 13C/cm 16C/cm2

0.7

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

2.1

2.4

2.7

3.0

Current density (A/cm )

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)