Lehigh University
Lehigh Preserve
US-Japan Winter School
Semester Length Glass Courses and Glass Schools
Winter 1-1-2008
Lecture 4, Part 1: Proton conduction in glass sand
its application to fuel cell - Proton conduction
Masayuki Nogami
Nagoya Institute of Technology, Japan
Follow this and additional works at: http://preserve.lehigh.edu/imi-tll-courses-usjapanwinterschool
Part of the Materials Science and Engineering Commons
Recommended Citation
Nogami, Masayuki, "Lecture 4, Part 1: Proton conduction in glass sand its application to fuel cell - Proton conduction" (2008). USJapan Winter School. 11.
http://preserve.lehigh.edu/imi-tll-courses-usjapanwinterschool/11
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Proton conduction in glass and its application to fuel cell
Masayuki NOGAMI
Department of Materials Science and Engineering,
Graduate School of Engineering,
Nagoya Institute of Technology
Email: [email protected]
Home Page: http://nitzy.mse.nitech.ac.jp/~nogamilab/index.html
★
New optical glasses
★ Fast proton conducting glasses and their application to fuel cell
★ Self-assembling of nanoparticles
(b)
(a)
400
x1
x150
500
600
Wavelength
700
(nm)
800
Intensity (a. u.)
Optical memory
Nonlinearity
Fluorescence intensity (Arb. units)
Optics, Rare-earth
Proton Conductor
Fuel Cell
λ ex = 8 0 0 n m
λ ex = 2 6 7 n m
600
640
68 0
(S/cm)
560
W a v e le n g th (n m )
Metal Nanoparticles
o
Temperature ( C)
A
tip
R 2 ,C 2
Au
Si substrate
1
40
0.9
35
0.8
30
0.7
25
0.6
20
0.5
15
0.4
10
0.3
0.2
5
0
20
40
60
80
0
100 120 140
2
Current Density (mA/cm )
2
shell R 1,C 1
V
Cell Voltage (V)
Au Nanochains
Au Nanoparticles
Glass Electrolyte
Power Density (mW/cm )
Fuel cell
Sensors
log Conductivity
-0.5
150 100
50
0
-50
-75
-1
-1.5
-2
-2.5
-3
-3.5
-4 2
3
4
(Temperature, K)-1
5
x10 -3
Fluorescence
Spectral Hole-burning
PSHB spectrum in Eu3+-doped glass
0 0 1 0 1 0
Intensity (a. u.)
Hole
1 0 1 0 1 0 0 0
Laser
Rare-earth
in
Glasses
λex= 800 nm
λex= 267 nm
560
600
640
680
Wavelength (nm)
Faraday rotation
Self-Assembling of Nano-Particles and Nonlinear Optics
Shape-Control
(a. u.)
Spectral Hole-burning
A
R 2 ,C 2
Intensity
tip
V
Au
shell R 1,C 1
Si substrate
600
800
1000 1200
Wavenumber
1400 1600
(cm-1)
1800
Nanoparticles
Self−Assembly
-5
0
5
10
15
Delay time (ps)
80
χ
(3)
(10
-11
esu.)
Normalized ∆T/T (a.u.)
Pump power: 30 mW
120
40
0
500
600
700
Wavelength (nm)
800
Morphology-Control
Proton conduction in glass and its application to fuel cell
(S/cm)
• Introduction
Possibility of fast proton conduction in the glass
• Sol-gel method for preparation of proton conducting glasses
Mechanism of proton conduction in porous glass
Glasses and films exhibiting high proton conductivities at
150oC ~ -100oC
• Applications
Fuel
cell
Electrolytes
for gas sensor and fuel cell
Sensors
• Conclusions
o
Temperature ( C)
150 100
1
-3
40
-3.5
Cell Voltage (V)
35
30
0.7
25
0.6
20
0.5
15
0.4
10
0.3
5
60
80
0
100 120 140
2
Current Density (mA/cm )
2
40
-75
-2
-4 2
20
-50
-2.5
0.8
0
0
-1.5
0.9
0.2
50
-1
Power Density (mW/cm )
log Conductivity
-0.5
3
4
(Temperature, K)-1
5
x10 -3
High proton conducting glasses for the fuel cell electrolyte
Stack
Electrode
Catalyst
Cells
Electrolyte
Electrode
H2
Electrolyte
-
+
+ O2
+
Anode
H2
2H+ + 2e-
Cathode
2H+ + 1/2O2 + 2eTotal
H2 + 1/2O2
H2O
H2O
High efficiency, Clean energy
Proton conducting membrane
Perfluorosulfonate ionomers (Nafion)
High proton conductivity at around
room temperature
Degradation in thermal and chemical
attacks
Inorganic Sol-gel-derived Glass
High proton conductivity at temperatures
of 150oC to -30oC
High stability against the thermal and
chemical attacks
Fast proton conducting-glasses prepared by the sol-gel process
• Mechanism of proton conduction in the solgel-derived porous glasses.
• Effect of pore structure on the proton
conduction.
• Preparation of glass films with ordered pore
structure.
• Application to the gas sensor and fuel cell.
Sample Preparation
Si(OC2H5)4
H2O,EtOH and HCl
Stirring
Drying at R.T.
Gel
Heat Treatment
Porous Glass
Porous structure of the sol-gel-derived glasses
O
H
H
O
O
H
OH
OH
H
O
H
O
H
O
H
O
H
O
H
O
O
H
O
OH
H
O
H
O
H
O
O
H
HO
HO
Glass
H
O
H
O
O
OH
OH
H
H
O
H
O
H
O
H
O
O
OH
H
O
H
O
H
O
HO
OH
H
O
H
O
O
H
O
H
O
H
O
OH
OH
H
O
H
O
H
O
O
4
-1
H
O
H
O
-1
H
O
H
O
H
O
OH
Pore
H
O
dV/d logr (cm3 nm g )
H
O
H
O
H
O
OH
H
O
H
H
O
H
O
Glass
HO
H
O
HO
H
O
O
H
HO
H
HO
H
O
H
O
H
O
HO
HO
OH
HO
H
O
H
O
H
O
H
O
OH
H
O OH H
O
H
O
H
O
H
O
H
O
O
H
H
O
H
O
H
H
O
H
O
H
O
O
H
O
H
O
H
O
H
O
OH
OH
Pore
H
O
H
O
H
O
H
O
O
H
H
O
O
H
O
H
O
H
O
H
O
H
O
OH
OH
H
O
H
O
H
O
H
O
H
O
H
O
H
O
O
SiOH bonds
Porous properties of the
glass
Surface Area
up to ~1000m2/g
Pore volume
0.1 ~ 0.5 cm3/g
Pore size
> 1 nm
H
O
H
O
H
O
H
O
H
O
H
O
H
O
OH
OH
H
O
Glass
H
O
H
O
O
H
O
HO
H
O
H
O
H
O
O
H
HO
3
2
1
0
1
10
Pore radius (nm)
Water molecules absorbed in the porous glasses
Hydrogen bonded
H2 O
Glass
Physically adsorbed
H2 O
HO
OH
H
Ｈ
OH
O
H Ｈ
H
O
HO H
O
O
H
O
H Ｈ
O
H Ｈ
O
H Ｈ
O
H
O
H Ｈ
O
H Ｈ
O
H
O
H Ｈ
O
H ＨH
Ｈ
H O O OH H O
O
H
O OH H
O
O
H
HO
Glass
H Ｈ
O
H
O Ｈ
OHH Ｈ
Ｈ
OH OH H O
O
H
H
O
O
H Ｈ
O
H
O Ｈ
H
O
H Ｈ H Ｈ
O
O
H
Ｈ
O
H
O Ｈ
H Ｈ
O
H Ｈ
O
HO
HO
OH
H Ｈ
O
H
O Ｈ
HO
HO
HO
HO
OOH
HH
O
OH
HO
HO
OH
O
OH H
H
OH O
HO
H
O H
O
O H
H
O
HO
OH
OH
H OH
H
H
H
O O
O O H
O H
O
O
O
H
H
O
HO
OH
H
HO HO O
HO
H
O
H
O
H
O
O
H
OHH O
H
O
H OH
H
OO
H
OO
OH
OH
HO
HO
H Ｈ
O
H Ｈ
O
H
O Ｈ
H
O
H Ｈ
OH
O
H
O
H Ｈ H Ｈ
OH O H
O
O
H Ｈ
H Ｈ
O
HO H
O
O
HO
H Ｈ H
O
O
H
O
H
O Ｈ
H Ｈ
O
O
H
H
Ｈ
OH
O
H Ｈ
H
H
O
O
H Ｈ
O H
H Ｈ H
O O O
H Ｈ
O H
O
H
H Ｈ
O
O
H
O Ｈ
H
O
O
H
H
O
OH
H
OH O
H
O
OH
H
HO O
O
H
H OH HO
HO O
HO
HO
O
Physically adsorbed
H2O molecules are
removed by heating
at around 100oC.
H
O Ｈ
H Ｈ
O
H
H O
O
H
O
H H
O O
H
O
OH
H
O
OH
OH
HO
H
HO H
O O
H
O
H
HO O
H
O
H
O
SiOH
Physically
bonds
adsorbed
H2 O
H
HO
O
HO
HO
H
O
H
O
H
O
H
O
OH
OH OH
H
H
O
O
HH O
H H
O
O O
H H
H O
O
OH O
O
HO H
H
O
H
O
H
O
H
O
O
H
O
H
OO
H
H
O
H
H H OH
O H
O H
O HO O
O
O
H
O
O
H
HO
Glass
HO
O
OH
OH
H
OH O
H
O
OH
HO
OH
H
O
Glass
OH
He
ex o ati
po r ng
su
re
O
O
H
HO
H Ｈ
O
H
Ｈ
O
H Ｈ
H Ｈ
O O
H Ｈ
O
H Ｈ H
O
O
H Ｈ
H
Ｈ
H ＨO
O
H
H Ｈ
H O
O Ｈ
Ｈ
O
O
H H Ｈ
O ＨO
H
Ｈ
O
H Ｈ H Ｈ
H Ｈ
O
O
O
H
OH
O
H Ｈ
OHH Ｈ
Ｈ
O
OH OH H O
O
H H Ｈ
H
O
O
O
Ｈ
H
O
H
H ＨH
Ｈ
H O O OH H O
O
O
H
H
O OH H
O
O
H Ｈ
O
H Ｈ
O
H Ｈ
O
H Ｈ
H Ｈ
O
H O
H
Ｈ
Ｈ
O
O
H Ｈ
O
H Ｈ
O
H Ｈ
O
H Ｈ
O
H Ｈ
OH
O
H
O
H Ｈ
HO H
O
O
H
O
H
O
H Ｈ
O
H
O
H
O
SiOH bonds
H Ｈ H Ｈ
OH O H
O
O
H
O Ｈ
H Ｈ
O
H Ｈ
O H
H Ｈ H
O O O
H Ｈ
O H
O
H
H Ｈ
O
O
H Ｈ
O
O
H
H
O
O
H Ｈ
O
H
O Ｈ
H
O
Exposure
to humid
atmosphere
HO
O
H
Effect of the physically bonded H2O molecules
on the conductivity
-7
(S/cm)
-3
3
Z" ( x10 Ω)
-4
-2
2nm-glass
-1
-8
4
1
Weight gain
0
0.8
-1
0.6
-2
σ
Normalized weight gain
1
3
0.4
Conductivity
0.2
0
log
2
3
Z' ( x10 Ω)
(S/cm)
1
-3
-4
0
10
20
30 40 50 60
Time
(min)
70
-5
80
log
0
σ
4nm-glass
0
-9
-10
0.6
0.8
1
log [H2O]
log σ = K log [H2O]
1.2
Controlling the amount of the chemically bonded H2O molecules
O
H
H
O
O
H
OH
OH
H
O
H
O
H
O
H
O
H
O
H
O
O
H
O
OH
H
O
H
O
H
O
O
H
HO
HO
H
O
O
OH
Ｈ
OH H O
H
O
H
O
H
OH
H
O
H
O
O
H
O
OH
OH
H
O
H
O
H
O
O
H
O
H
O
H
O
H
O
H
O
H
O
H
O
H
O
H
H
O
H
O
O
H
HO
OH
OH
H
O
H
O
H
O
H
O
H
O
H
O
OH
OH
H
O
H
O
H
O
O
H
O
HO
O
H
OH
OH
H
O
H
O
H
O
H
O
O
H
HO
H
O
H
H
O
H
O
H
O
H
O
H
O
H
O
O
H
O Ｈ
Ｈ
O
H
O
HO
H
O
H
H
O
HO
O
O
H
H
Pore
O
O
HO
HO
HO
H Ｈ
O
O
H
O
Ｈ
O
H
H
O
H
H
H
O
H
O
H Ｈ
O OH
H Ｈ
O
H
O OH H
O
H
O
H
O
H
O
Ｈ H
H
O O
H
O
H
O
H
O
H
O
H Ｈ
O
O
H
O
H ＨH
H OO
O
H
O
H
O
OH
OH
H
O
H Ｈ
O
H
O
H
O
H
O
H
O
H
O
H
O
H
O
H
H
O
H
O
O
H
H
O
OH
OH
H Ｈ
O
H
O
H Ｈ
OH
O
H
O
at around 200oC.
H
O
H
O
O
H Ｈ H
O O
H
O
H Ｈ
OH
O
H
O
Chemically bonded
H2O molecules are
removed by heating
Glass
Effect of the chemically bonded H2O molecules
on the conductivity and its activation energy
Activation energy (kJ/mol)
(Scm -1 )
-11.5
-12
σ
160oC
log10
-12.5
310oC
-13
log σ (S/cm)
at 150oC
-11
1.8
210oC
250oC
2
2.2
2.4
2.6
2.8
1/Temperature (K)
x 10-3
-12
-13
-14
120
100
80
60
-1
-0.5
0
0.5
1
log [H2O]・[H+]
-15
-16
-1
-0.5
0
0.5
1
log σ = k log [H2O]・[H+]
log [H2O]・[H+]
E = k log [H2O]・[H+]
Proton conduction in the porous
glass
Activation energy (kJ/mol)
120
100
Conduction process of proton
through the porous glass
Chemically
bonded H2O
80
E
60
Physically
bonded H2O
40
HH
O
H+
20
0
0
1
log10 {[H] [H 2 O]}
2
(mol/l)
3
O
Si
O
HH
O
HH
O
HH
O
H+
H
O
Si
O
O
Si
O
H
O
Si
O
HH
O
H+
O
Si
O
Proton conduction is controlled by
the proton dissociation from the
SiOH bond and the proton hopping
between SiOH and H2O.
Fast proton conducting-glasses prepared by the sol-gel process
• Mechanism of proton conduction in the solgel-derived porous glasses.
• Effect of pore structure on the proton
conduction.
• Preparation of glass films with ordered pore
structure.
• Application to the gas sensor and fuel cell.
Preparation of glasses with different pore size
Si(OC2H5)4
Catalysts
Templates
H
y d r o ly z in g
Reacting
Drying
Pore size
Gels
B u lk
G la s s
Heating
Porous Glasses
5 cm
6
4
No. 3
No. 2
No. 1
No. 4
(S/cm)
-2
2
0
1
2
5 10 20 50
Pore Diameter (nm)
log conductivity
3
-1
dV/d(logD) (cm .g nm-1 )
Pore size distribution and its effect on the conductivity
-4
No. 2
No. 1
-6
-8
No. 3, 4
-10
-12
40
60
Relative humidity (%)
80
DTA curve for No. 2 glass
No. 3
6
No. 2
Solidification of H 2O
o
Exotherm
= -45 C
4
2
Quantum dot
effect
-60
0
1
-40
-20
0
o
Temperature ( C)
o
20
Temperature ( C)
30
0
-30
2
5 10 20 50
Pore Diameter (nm)
-1
log σ (S/cm)
3
-1
dV/d(logD) (cm .g nm-1 )
Effect of the pore size on the proton conductivity
No.2
-2
-3
No.3
-4
3.2
3.4
3.6 3.8 4
-1
1000/T (K )
4.2
4.4
Effect of P2O5 on proton conductivity
Si(OC2H5)4
Hydrolyzing
PO(OCH3)3
Reacting
Drying
P5+ ion
Gels
Heating
Porous Glasses
FT-IR
Glass Composition
P2O5-SiO2 glass
SiO2 glass
H
Absorption coefficient
4000
O
H
Si -OH O
3500
3000
2500
2000
Wave Number ( cm-1)
Dissociation energy
for proton;
SiOH > POH
H
Absorption coefficient
(cm-1)
P -OH
(cm-1)
H
4000
3500
3000
2500
Wave Number ( cm-1)
High proton conductivity
can be expected for POH
bonds.
2000
•
High proton conductivity
in wide temperature
range
-30oC to 150oC
(ex. 170 mS/cm at 150oC)
o
Temperature ( C)
150 100 50
0
(S/cm)
proton dissociation from the
SiOH bond and the proton
hopping between SiOH and
H2O.
-1
0
-50
-75
Sol-gel glasses
-2
Nafion
-3
log Conductivity
•
Dependence of Conductivity on
Temperature
Proton conduction
mechanism
-4
-5
-6
Glasses
-7
-8
2
3
4
(Temperature, K) -1
5
x10 -3
Fast proton conducting-glasses prepared by the sol-gel process
• Mechanism of proton conduction in the solgel-derived porous glasses.
• Effect of pore structure on the proton
conduction.
• Preparation of glass films with ordered pore
structure.
• Application to the gas sensor and fuel cell.
Sol-Gel Method for Glass
Preparation Preparation
of pore-oriented glass films
Si(OC2H5)4
Pore
orientation
Hydrolyzing
Templates
Catalysts
Reacting
Pore size
Drying
Thin Film
Gels
Bulk Glass
Heating
200nm
Substrate
Porous Glasses
5cm
Pore-oriented glass films by self-assembling method
Preparation of glass film by self-assembling method using templates
Substrate
Solution
Film
Substrate
Film
Pore
CTAB;
(CH3(CH2)15N+(CH3)3Br
Dipping
Heating
Gel
C16EO10;
(C16H33(OCH2CH2)10OH
Porous glass film
Self-assembled pore-oriented glass films
210
Glass film
200
d(nm)
4.75
4.44
4.18
a=9.50 nm
(b) hkl d(nm)
100 2.98
a=2.98 nm
Sub.
Cubic
(a) C16EO10
(b) CTAB
2
200 nm
100
Intensity (Arb. units)
211
(a) hkl
200
210
211
3
4
2θ (degrees)
5
6
Hexagonal
Conductivities of pore-oriented glass films
I
V
-4
10
log σ
(S/cm)
-5
-6
(a) C16EO10
-7
-8
I
-9
(b) CTAB
V
-10
-11
40
50
60
70
80
Relative Humidity (RH %)
90
Fast proton conducting-glasses prepared by the sol-gel process
• Mechanism of proton conduction in the solgel-derived porous glasses.
• Effect of pore structure on the proton
conduction.
• Preparation of glass films with ordered pore
structure.
• Application to the gas sensor and fuel cell.
Application of proton conducting
glasses
Sensors
Hydrogen, Humidity
EMF
e-
PHII
H2 = 2H+ + 2e-
H+
PHI
2H+ + 2e- = H2
EMF =
RT
nF
ln
PHII
PHI
Responsibility to H2 gas
80
60
50
60
100
PHII
=25
PHI
40
40
20
0
-20
20
0
n=2
0.0
1.0
2.0
3.0
4.0
5.0
ln (P )
1
0
EMF ( mV )
EMF (mV)
80
H
20
40
Time (min)
60
EMF = (RT/nF) ln(PH)
H2 = 2H+ + 2e-
Gas sensors ~ Preparation of thin films ~
Solid electrolyte
( 組成 : 5P2O5-95SiO2 )
Si(OC2H5）4, 2-PrOH, HClaq
HClaq
H3PO4
Brij56
Spin coating
Alcohol
vapor
Pt
Glass film
Manganese Oxide
ITO glass substrate
Air or Ar
25 oC
Glass film
Reference electrode
MnO2+4H++2e- ↔Mn2++2H2O
ITO substrate
MnO
Intensity (a.u.)
P/G stat
Heat treatment (400oC,4h)
2
20
30
40
50
60
2θ / deg (Cu-Kα)
70
Gas sennsing
0.2
o
25 C
1%CH3OH vapor in air
0.3
1%H2
EMF / V
0.2
EMF / V
o
25 C
0.1
1%CH3OH vapor
1%C2H5OH vapor
0.1
0.5%NH vapor
3
1%CH COCH vapor
3
0
0
10
3
20
30
Time / Sec
40
50
0
0
500
1000
Time / Sec
1500
High proton conducting glasses for the fuel cell electrolyte
Stack
Electrode
Catalyst
Cells
Electrolyte
Electrode
H2
Electrolyte
-
+
+ O2
+
Anode
H2
2H+ + 2e-
Cathode
2H+ + 1/2O2 + 2eTotal
H2 + 1/2O2
H2O
H2O
High efficiency, Clean energy
Proton conducting membrane
Perfluorosulfonate ionomers (Nafion)
High proton conductivity at around
room temperature
Degradation in thermal and chemical
attacks
Inorganic Sol-gel-derived Glass
High proton conductivity at temperatures
of 150oC to -30oC
High stability against the thermal and
chemical attacks
Fuel Cell
1
60
50
Cell voltage (V)
0.8
40
0.7
0.6
30
0.5
20
0.4
10
0.3
0
250
0.2
0
50
100
150
200
2
Current density (mA/cm )
2
0.9
Power density (mW/cm )
2
50.7 mW/cm
Conclusions
•
Fast proton-conducting porous glass
+ Preparation by the sol-gel method
Porous glass with large surface area and small-sized pores
+ Proton conduction process
Dissociation of the protons and their hopping between
water molecules and hydroxyl groups
•
High proton conductivities
+In wide temperature range from -30oC to 150oC
ex. 170 mS/cm at 150oC
•
•
Glass films having high-ordered pore structure
Possible application as the electrolyte
+ Sensor and Fuel cell
Thank you