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New Polymer Electrolytes

Morton Litt
Case Western Reserve University
14 November 2001
New Polymer Electrolytes
Rigid-rod, nematic liquid crystalline polyimides:
Special Requirements homopolymer or copolymers.
O
• High proton conductivity with low sensitivity to relative humidity. O O SO3H O
N N N N Ar
The conductivity should be about 1.0E-3 S/cm at 15% RH. x
O O SO3H O O z
• Fuels and reactants such as hydrogen and oxygen should
have essentially no permeation through the PEMs.
Molecular Design
• Can be directly cast on electrode as PEM in MEA processing.
The rigid-rod liquid crystalline feature enables a
• High chemical, dimensional, and mechanical stability during the
few bulky or angled comonomer units to separate
preparation and under the working conditions of the micro-fuel the polymer chains over their whole length. This
cell.
creates permanent pores lined with SO3H groups.
Water is held very strongly
Categories and structures of comonomers.
(a) N H2 N H2 PDA

(a). Homopolymer SO3H SO3H
or copolymer
O
C H2O SO3H SO3H H2O SO3H SO3H
N H2 N H2 N H2 N H2 N H2 N H2
with linear, small
C
O
X X
comonomer SO3H SO3H
DBB X= H, (3P)TDA; X= H, (DBPP)DA;
X= , (4P)TDA X= , (DBPDP)DA
SO3H
(b) R R
(b).Copolymers
with linear, H2O H2O H2O SO3H
H2O H2O SO3H
bulky comonomer
N H2 N N N H2
N H2 N H2

X
2BF4 R=H, NHA;
SO3H
X= H, (DNP)DA; R=CH3, NMA;
R R
X= , (DNDP)DA R=OCH2CH3, NEA

H2 N N H2
SO3H SO3H

(c) N H2 N H2
(c). Copolymers SO3H SO3H SO3H
H2O H2O H2O H2O
FDA
O
ODA with angled, H2O H
3
random (R) or and/or rigid SO SO3H
RF5 mole% of comonomer H2O H
block (B) comonomers SO
3

copolymers comonomer, NH2-Ar-NH2
New Polymer Electrolytes
Measured interchain spacings of selected polyimides.
Equatorial Meridional The XRD patterns of oriented
Polyimide diffractions, (Å) Diffractions, (Å) polyimide fibers show typical
dH12 dH2 dV1 dV2 dV3 nematic liquid crystalline packing
Homopolymer 6.03 3.74 16.60 8.06 5.43 (I). The d-spacing of the first
1
a BP10(18/2) 5.83 3.70 8.11 5.50 equatorial diffraction peak
corresponds to the polymer
b1 RF5 6.46 3.68 8.06 5.46
interchain spacing (II). As shown
RO5 6.32 3.74 8.08 5.52
R(3P)T5 6.23 3.74 8.09 5.47 in theTable, copolymers with
c 1 angled or bulky comonomers have
R(4P)T5 6.14 3.78 8.11 5.49
Fiber direction

larger interchain spacings than
RNMA5 6.21 3.81 7.95 5.50
1: homopolymer and the copolymer
a. linear, small comonomer; b. angled comonomers; with linear, small comonomer.
c. linear, bulky comonomers.
(I) 2
: The interchain spacing.

1e+0
dH1 1
1e-1

Conductivity (S/cm)
Conductivity (s/cm)
SO3H

SO3H

SO3H

1e-2
SO3H

Homopolymer
0.1
RF5
1e-3
RO5
SO3H

R(4P)T5
SO3HSO3H SO3H
SO3H

SO3H

RD5 RF5
1e-4
SO3H

Nafion Nafion

0.01
1e-5
20 30 40 50 60 70 80
0 20 40 60 80 100 (a) Temperature ( C)o (b)
SO3H

Relative Humidity (%)
SO3H

(a). Room temperature proton conductivities of polyimides with bulky or angled
comonomers are about that of Nafion® between 35-75% RH, but higher at 15% and 100%
SO3H

RH. At 15%RH, the conductivities are around 1.0E-3 S/cm. (b). High temperature proton
(II) conductivity of RF5 at 100% RH increases with temperature, in contrast to that of Nafion®.
New Polymer Electrolytes

100
14
96
12 Homopolymer Temperature of maximum
RF5
RO5
water loss rate.
10 92
R(4P)T5 o
R(3P)T5 Polymer Tmax ( C)

W t%
8 Homopolymer
88
λ

BP10(8/2)
RF5 Homopolymer 92.9
6
84 BP10(18/2) BP10(18/2) 90.1
4
R(4P)T5 R(4P)T5 105.9
80
2
(a)
Tmax (b) RF5 104.7
0 76
0 20 40 60 80 100 120 0 50 100 150 200 250 300
o
Relative Humidity (%) Temperature ( C)

Figure (a). Room temperature water uptake capacities of polyimides, measured by weighing
method. (b). TGA curve of polyimides. The polymers were preconditioned at 23oC, 35-45%RH. The
derivative curve shown is for homopolymer. Tmax is indicative of the water activity in the polymer; the
lower the activity, the higher the temperature at which water is desorbed rapidly. The change of 10
to 15oC in maximum rate means that at a given temperature, water activity in R(4P)T5 is about 50%
of that in homopolymer.
New Polymer Electrolytes

1

Conductivity (S/cm) 0.1

0.01

1E-3
Homo-T300-15 RT
1E-4 Homo-T300-15 40
Homo-T300-15 60
1E-5 Homo-T300-15 80
Nafion
1E-6
0 20 40 60 80 100
Relative Humidity (% )

Elevated temperature conductivity of crosslinked homopolymer (300oC, 15 min.)
at different relative humidities, compared with Nafion.
New Polymer Electrolytes
• Accomplishments
1. The polymers normally had conductivities of 0.1 to 0.4 S/cm at 100% RH, higher than
Nafion. The best copolymers, with large cross-section comonomers, had conductivities
up to 1.5*10-3 S/cm at 15% RH, 20 to 30 times higher than Nafion.
2. Under ambient conditions the film moduli were usually between 1.5 and 3 Gpa with
elongations at break between 7 and 25%. The polymers were easy to handle. We
routinely got inherent viscosities of >4 dL/gm.
3. Polymers could thermally cross-linked by heating for ten to fifteen minutes at 300oC.
Some photocrosslinking was attempted but the high UV absorption of the copolymer
interfered with the crosslinker absorption and decreased cross-linking efficiency.
4. Conductivity at 15% RH of linear copolymers containing large amounts of non-polar
comonomer (33 to 50 mole%; physical properties stable even in hot water), could
decrease to below 10-6 S/cm. When an angled or bulky comonomer was also present,
conductivity at 15% RH dropped compared to our best materials, but still remained
above 10-4 S/cm.
5. Polymers thermally cross-linked at 300oC had water stability, though with some loss of
acid groups and of low humidity conductivity. Conductivity at 100% RH in these systems
was almost unaffected, remaining above 0.1 S/cm. Conductivity at higher temperatures,
up to 80oC, rose to where it was about that of the un-crosslinked polymer at that
temperature and relative humidity. They were close to 0.1 S/cm at 80oC and 50% RH.
6. While the polymer films swelled in thickness as relative humidity increased, the lateral
swelling was under 8% even at 100% RH. Cross linking could produce high conductivity
films with very little swelling, even in water.