Electrochemical Hydrogen Pumping
24
Kayley Fishel, Guoqing Qian, Glenn Eisman,
and Brian C. Benicewicz
24.1 Introduction
The concept of using electrochemical reactions
with polymer-based proton exchange membranes
to separate, purify, and compress hydrogen was
an unobvious outcome of the effort to develop
power generation solutions for satellites and
spacecraft in the United States in the 1950s.
With the development of membrane-based fuel
cell technology by General Electric in the 1960s
and 1970s [1, 2], applications in hydrogen and
related alkali ion-intensive processes [3] were a
natural fallout of their programs. Included in the
list of such applications besides fuel cells were
the chlor-alkali membrane process, water elec-
trolysis, oxygen concentrators, and electrochem-
ical hydrogen pumping/concentrators (EHP).
Furthermore, the development of Nafion®
(registered trademark of DuPont) ion exchange
membranes was also an outcome of this period
and remains the primary membrane separator for
all of the above applications to date though this is
being challenged by a new class of materials
K. Fishel • G. Qian • B.C. Benicewicz (*)
Department of Chemistry and Biochemistry, University
of South Carolina, 541 Main Street, Horizon 1 Room 232,
Columbia, SC 29208, USA
e-mail: benice@sc.edu
G. Eisman
H2Pump LLC, 11 Northway Lane North, Latham, NY
12110, USA
# Springer International Publishing Switzerland 2016
Q. Li et al. (eds.), High Temperature Polymer Electrolyte Membrane Fuel Cells,
DOI 10.1007/978-3-319-17082-4_24
capitalizing on high-temperature membranes,
the topic of this chapter.
Electrochemical hydrogen pumping was first
reported by Maget [4] while developing the SPE
(Solid Polymer Electrolyte, the original descrip-
tion of the membrane and electrode technology
prior to “PEM” terminology) family of electro-
chemical processes. Specifically it was found
that a proton generated during the oxidation of
hydrogen at the anode would recombine into
“new” molecular hydrogen at the cathode after
the proton was driven through the membrane by
an applied potential (Fig. 24.1). For this process
to work, other reaction chemistries at the cathode
had to be eliminated, e.g., the oxygen or halide
reduction reactions. Though this was a unique
application of hydrogen oxidation-reduction
chemistry, the hydrogen pump process never
materialized as a useful concept and remained
an intellectual and academic curiosity until
recently. Applications and concepts which have
emerged include hydrogen pumping, hydrogen
separations, as well as adiabatic hydrogen com-
pression. It has only been in recent years that
practical applications have been, or are now
under development for industrial and alternative
energy applications. Furthermore, this technique
has been found to be a useful electrochemical
analytical tool for studying electrode perfor-
mance in such devices as fuel cells and water
electrolyzers [5].
527
528
H2 Separation Process
Power Supply
Anode
e
e Total reaction : H2 ðanodeÞ
Hydrogen
H2 2H+ 2H+ + 2e-
H2O (V) + H2O (V)
Membrane
Electrodes
H2 H2
Fig. 24.1 Hydrogen membrane-based electrolysis
Recently, with the development of new high-
temperature proton exchange membranes, as
well as the increased interest in hydrogen-related
technology and applications, there has been a
resurgence of interest in EHP. Companies have
formed to apply the process in both industrial and
emerging hydrogen applications. There has also
been an increase in the technical literature and
conference presentations, and government (state
and federal) agencies have included this technol-
ogy in recent solicitations. These activities are
partly due to membranes such as polybenzi-
midazoles (PBI), which have become available.
This chapter will focus on the development of the
high-temperature membrane-based electrochem-
ical hydrogen pumping process.
24.2 Electrochemistry
The basic working principle of the electrochemi-
cal hydrogen pump process is that hydrogen
molecules enter the anodic compartment of an
electrochemical cell and are oxidized to protons
and electrons within the catalyst layer of the
electrode. The protons are driven through the
ion exchange membrane while the electrons
pass through the external circuit to the cathode
as a result of the applied voltage to the
electrodes. The protons and electrons then
recombine at the cathode electrode to (re-)form
molecular hydrogen. The overall chemical
reactions are described by (24.1–24.3).
K. Fishel et al.
Anode : H2 ! 2Hþ þ 2e ð24:1Þ
Cathode : 2Hþ þ 2e ! H2 ð24:2Þ
Cathode
! H2 ðcathodeÞ ð24:3Þ
H2
The cell voltage between the anode and cathode
is given by (24.4). The Nernst potential ENernst, is
given by the Nernst equation (24.5), where
Eo is the standard potential of a hydrogen reac-
tion, R is the gas constant, T is the temperature in
Kelvin, F is Faraday’s constant, pcathode and
panode are the partial pressures of hydrogen at
the anode and cathode, respectively.
E ¼ ENernst  Epolarization  Eohmic ð24:4Þ
RT pcathode
ENernst ¼ Eo  ln ð24:5Þ
2F panode
The polarization overpotential (Epolarization) is the
sum of the polarization overpotentials at the
anode and cathode and given by the
Butler–Volmer equation. At low overpotentials,
the polarization overpotential can be
approximated by (24.6), where R is the gas con-
stant, T is the temperature in Kelvin, F is the
Faraday’s constant, i is the current density, and
i0 is the exchange current density.
RT i
Epolarization ¼ ð24:6Þ
2F i0
The ohmic overpotential Eohmic is the potential
loss due to cell ohmic resistances and given by
Ohm’s law (24.7), where i is the current density,
Rohmic is the cell ohmic resistance, which
includes membrane resistance, electrode resis-
tance and cell hardware resistance.
Eohmic ¼ iRohmic ð24:7Þ
24.3 Low- and High-Temperature
Devices
Just as the type of electrolyte membrane
influences operational conditions and perfor-
mance in fuel cells, the ion exchange membrane
24 Electrochemical Hydrogen Pumping
used in hydrogen pumping applications affects
the design and efficiency. Both low-temperature
and high-temperature devices have been used or
are under development for hydrogen separation
and purification using this technique. In the
low-temperature devices, the perfluorosulfonic
acid family of membranes, e.g., Nafion®, are ion
exchange membranes with sulfonic acid groups
directly bonded to the polymer. Devices
containing these types of membranes operate at
low temperatures (typically ~50–80  C). Further-
more, the membranes need to be hydrated to
support proton conduction [6]. A disadvantage
of these membranes is the tendency of water to
collect in the electrode layers and flow fields of
the plates resulting in an undesirable “flooded”
state. The result is a decrease in performance due
to the reduced electrode active area. Among
others, an additional disadvantage of the
low-temperature cells is that the tolerance to
selected impurities, e.g., carbon monoxide, at
the electrode is low resulting in a (reversible)
degradation process. This limits the utility of
such devices in hydrogen separation and purifica-
tion applications. Some of these obstacles in
low-temperature devices can be overcome by
using membranes that are able to operate at
higher temperatures. Early high-temperature-
based hydrogen purification was initially shown
feasible using traditional phosphoric acid fuel cell
(PAFC) technology [7]. High hydrogen recovery,
high hydrogen purities, and tolerance to tradi-
tional fuel cell impurities were demonstrated
using PAFC stack technology. In the 1990s, phos-
phoric acid-doped polymer membranes that
offered similar increased tolerance to gas
impurities were explored [8]. Operating at high
temperatures (>100  C) with phosphoric acid as
the electrolyte requires a polymer membrane that
is both thermally stable and chemically resistant.
Since polybenzimidazoles (PBIs) demonstrate
both of these qualities and have shown excellent
stability under these conditions when used in fuel
cells, PBI was a candidate for use in hydrogen
pumping applications. Operating at these high
temperatures also increases the platinum catalyst
tolerance to carbon monoxide and other
impurities, and thus becomes an enabling feature
529
in some applications. An additional advantage of
high-temperature operation is that flooding of the
electrodes with water is minimized, as water
exists only in the gas phase at normal operating
conditions. The chemistry of the polymer mem-
brane influences the pump efficiency just as it
influences the performance of a fuel cell. Various
chemistries of PBI have been studied in hydrogen
pumps to understand how the chemistry affects
electrical efficiency, power consumption, dura-
bility of the membrane electrode assemblies,
and gas purification.
24.4 High-Temperature Membrane
Hydrogen Pumping
24.4.1 Para-PBI
Poly(2,20 -( p-phenylene)5,5 0 -bibenzimidazole)
(para-PBI) has been tested by various research
groups for high-temperature hydrogen pumping.
In 2007, Perry et al. [9] reported the use of a para-
PBI membrane prepared through the poly-
phosphoric acid process or PPA process [10] to
be used as the polymer electrolyte membrane in
an electrochemical hydrogen pump. Further
information on the PPA process can be found in
Chap. 10. Studies were performed using various
gas mixtures, and operations were performed
with and without external humidification in
order to understand the power requirements,
membrane electrode assembly (MEA) durability,
and purification and electrochemical efficiencies.
These para-PBI polymers had inherent
viscosities (IV)s between 2.7 and 3.7 dL g1
and acid doping levels of 34.9–39.1 mol phos-
phoric acid (PA) per mole polymer repeat unit
(PRU) [9]. Tests were initially performed with
pure hydrogen and without external
humidification at the anode. Polarization curves
of the hydrogen pump are shown in Fig. 24.2.
The curves exhibited a linear relationship
between voltage and current, which
demonstrated reversibility, up to at least
1 A cm2. At a typical operating current density
of 0.2 A cm2, electrochemical hydrogen
pumping required relatively low voltages, i.e.,
530 K. Fishel et al.

Fig. 24.2 Polarization

curves (scan rate
1.4 mA s1) of an 200
electrochemical pump
operating on pure hydrogen
at 160  C, constant flow
rate 94 mL min1. 150

Voltage (mV)
Reproduced from [9] with
permission of Elsevier

100

50

0
0.0 0.2 0.4 0.6 0.8 1.0
Current Density (A/Cm2)

Fig. 24.3 Long-term 30

operation of a hydrogen
pump at 0.2 A cm2, 1.2
stoichiometric flow of pure 25
hydrogen, 160  C.
Reproduced from [9] with
permission of Elsevier
20
Voltage (mV)

15

10

0
0 500 1000 1500 2000
Lifetime (hrs)

45 mV at 160  C. The current efficiency of the
electrochemical pump was conducted by measur-
ing the cathodic outlet hydrogen flow at varying
current densities. The relatively high current
efficiencies, greater than 83 % from 0 to
2 A cm2, were achieved, showing high
efficiencies under non-humidified conditions.
The durability of the electrochemical pump was
investigated at constant current density of
0.2 A cm2 at 160  C operating on pure hydro-
gen with no external humidification and the volt-
age was found to be relatively constant at 22 mV
for over 2000 h of operation as shown in
Fig. 24.3.
The effects of relative humidity were then
studied by cycling the relative humidity between
0 and 3 % at 160  C. There were no large changes
seen in the voltage by changing the relative
24 Electrochemical Hydrogen Pumping
350
300
250
Voltage (mV)
200
150
100
50
0
0.0 0.3 0.5
Current Density (A/cm2)
Fig. 24.4 Polarization curves for non-humidified
conditions (solid squares) at 1653 h and humidified
conditions (unfilled squares) at 2144 h. The crosshairs
symbolize a humidified Nafion membrane operated at
70  C for comparison [11]. The hydrogen inlet feed
stream was adjusted to maintain 1.2 stoichiometric flows
humidity; the average voltage for non-humidified
conditions was approximately 33 mV and approxi-
mately 18 mV under humidified conditions.
Performance was found to be improved at 3 %
relative humidity when tested at 160  C. This
cell containing a para-PBI/PA membrane was
reported to have a lifetime of over 4000 h with
relatively stable voltages even under the stressful
conditions of alternating between humidification
and non-humidification. Power requirements were
tested for both humidified systems and
non-humidified systems by running polarization
curves at 160  C during each cycle. Figure 24.4
shows the polarization curves for the humidified
and non-humidified operations and includes
Nafion® (at 70  C) for comparison.
It can be seen that both tests performed using
para-PBI exhibit a near linear relationship.
Voltages at 0.2 A cm2 were 30 mV for the
non-humidified cell and 18 mV for the
humidified cell. Tests were also performed to
evaluate the ability of the pump to run on gas
streams contaminated with CO and CO2 and to
531
0.8 1.0 1.3 1.5 1.8 2.0
at each current density for the humidified polarization
curve. A constant flow of 75 mL min1 of hydrogen
was supplied up to a current density of 0.8 A cm2 and
then the current steps were continued at 1.2 stoichiometric
flow operation for the non-humidified polarization curve.
Reproduced from [9] with permission of Elsevier
evaluate the purity of the hydrogen produced at
the cathode when operated at 160  C. A gas
stream of 35.8 % H2, 11.9 % CO2, 1906 ppm
CO, and 11 % N2 was used at the anode and the
gas at the cathodic outlet was tested. Carbon
monoxide concentrations were reduced to
11–13 ppm and carbon dioxide was reduced to
0.19–0.37 %, showing that these pumps can
operate without high-purity hydrogen.
Kim et al. [12] later studied the effect of
platinum catalyst loadings on the efficiencies of
a H2/CO2 gas mixture (20/80 v/v) in cells
containing membranes composed of para-PBI
prepared through the PPA Process. Having the
ability to reduce the amount of platinum used for
catalysis in hydrogen pumping could signifi-
cantly reduce material costs. Electrodes
containing 1.1 and 0.2 mg cm2 were used at
the anode and cathode to produce four different
combinations of platinum loadings (1.1 mg cm2
at anode and cathode, 0.2 mg cm2 at anode and
cathode, 1.1 mg cm2 at anode and 0.2 mg cm2
at cathode, and 0.2 mg cm2 at anode and
532 K. Fishel et al.

Fig. 24.5 Polarization

curves for a hydrogen
pump using different levels
of Pt catalyst.
(PHP ¼ 1.1 mg cm2
at anode and cathode,
PHP-C ¼ 1.1 mg cm2
at anode and 0.2 mg cm2
at cathode, PHP-A ¼
0.2 mg cm2 at anode and
1.1 mg cm2 at cathode,
PHP-CA ¼ 0.2 mg cm2 at
anode and cathode).
H2/CO2 gas mixture
(20/80 v/v). Reproduced
from [12] with permission
of Elsevier

Table 24.1 Input and output of gases that were purified
through hydrogen pumping using a Celtec-P membrane at
160  C
Gas Input (%) Output
H2 50.5 99.896 %
CO 4.4 6.5 ppm
CO2 39 1010 ppm
CH4 6.1 18.7 ppm
1.1 mg cm2 at cathode) to study the effect of the
total platinum loading and the effect of a
decrease in platinum loading at both the anode
and cathode. Figure 24.5 shows the polarization
curves of the various platinum loadings on the
anodes and cathodes.
Compared to the MEA containing 1.1 mg cm2
of platinum at both the anode and cathode, the
MEA with lower platinum loading at the cathode
(0.2 mg cm2 at the cathode and 1.1 mg cm2 at
the anode) showed similar cell voltages up to
0.8 A cm2 while the MEAs that contained
lower platinum loading at the anode-side showed
significantly higher cell voltages during H2/CO2
separation. These results indicate that the large
overpotential seen in hydrogen purification using
a H2/CO2 gas mixture is due mainly to the hydro-
gen oxidation reaction at the anode; therefore,
the platinum loading at the cathode can be
reduced without significant loss in performance.
Petek et al. [13] investigated a commercial
Celtec-P-1000 MEA in a hydrogen pump at
temperatures in the 120–180  C range with
detailed investigations at 150  C. They analyzed
pumping characteristics using pure hydrogen, a
simulated SMR-WGS (steam methane
reforming-water gas shift) mixture of 70 %
hydrogen, 3 % carbon monoxide, 20 % carbon
dioxide, and 7 % methane, and a diluted hydrogen
mixture containing as low as 5 % hydrogen.
Hydrogen was separated quite efficiently from
the SMR-WGS mixture with an estimated power
requirement of 5 kW h kg1, which is much lower
than the estimates for conventional PSA (pressure
swing absorption) technologies. An adsorption
limited current of approximately 0.3 A cm2
was observed for the very dilute hydrogen
containing mixtures with 5 % hydrogen.
H2Pump LLC tested various gas mixtures in a
hydrogen pump with a Celtec-P membrane
[14]. When using a gas mixture containing
50.5 % H2, 4.4 % CO, 39 % CO2, and 6.1 %
CH4 at 160  C, hydrogen was able to be purified
to almost 99.9 % (Table 24.1).
Further testing was performed on a gas mix-
ture containing 1.12 % CO, 43.8 % CO2, with a
H2 balance using a Celtec-P membrane at 160  C
at 0.2 A cm2. The carbon monoxide was found
to be ~1 ppm at the outlet. These findings show
24 Electrochemical Hydrogen Pumping 533

Fig. 24.6 Purification 14,000

ratios for carbon dioxide 1.12% CO, 43.8% CO2, 23 C Dew Pt, Balance H2
and carbon monoxide at
12,000
various current densities
CO2 CO
using a Celtec-P membrane
at 160  C 10,000

Purification Ratio
8,000

6,000

4,000

2,000

0
0 0.1 0.2 0.3 0.4 0.5
A/cm2

Fig. 24.7 Polarization 100

curves measured at 160  C
for changing cathode gas 80
pressures (square ¼ 0 bar, 60
triangle ¼ 90 mbar,
circle ¼ 120 mbar) 40
Reproduced from [5] with
20
permission of Elsevier
U / mV

0
-20
-40
-60
-80
-100
0 0,1 0,2 0,3 0,4 0,5 0,6
j / A cm-2

the excellent purity that can be achieved using a
para-PBI membrane in a hydrogen pumping
device (Fig. 24.6).
24.4.2 Other PBIs
Huth et al. [5] performed hydrogen pumping tests
on a PBI membrane to study proton transport and
anode kinetics. Unfortunately, the source of the
material, type of PBI, and membrane acid doping
level were not specified. Polarization curves can
be seen in Fig. 24.7 and showed a nearly linear
behavior over the entire potential range
indicating that membrane resistance dominates
the overall cell resistance in this region.
The effects of temperature when the partial
pressure of hydrogen was held at 3 bar were
studied. When temperature increased, a larger
change in current was seen with changing
voltage showing an increase in conductivity
(Fig. 24.8). Huth et al. [5] went on to perform
many further experiments to study the proton
transport mechanism and anode kinetics
and found that the anodic )hydrogen oxidation
reaction follows the Volmer–Tafel mechanism
with the Volmer reaction being the rate-
limiting step.
534 K. Fishel et al.

Fig. 24.8 Polarization 120

curves of the proton pump
at various temperatures 90
with a hydrogen partial
pressure of 3 bar 60
(diamond ¼ 40  C,
circle ¼ 80  C,
30
triangle ¼ 120  C,
square ¼ 160  C).

U/mV
Reproduced from [5] with 0
permission of Elsevier
-30

-60

-90

-120
0 0,2 0,4 0,6 0,8 1
j / A cm-2

Thomassen et al. [15] also evaluated a
PBI-based membrane for EHP applications.
Again, the membrane source, type of PBI, and
membrane acid doping were not specified. Refor-
mate gas mixtures containing varying amounts of
hydrogen, carbon dioxide, carbon monoxide, nitro-
gen, and methane were used in a hydrogen pump
cell with good results. Current efficiencies up to
90 % were reported at high current densities, and
the cells were operated at a differential pressure of
0.65 bar. Significant reductions in gas impurities
were measured under stable operating conditions.
24.5 Low-Temperature Hydrogen
Pumping
Although the focus of this book is predominantly on
polymer membranes for use in high-temperature
devices, a few examples of polymer membranes
used in low-temperature hydrogen pumping have
been included in this chapter for comparison.
hydrogen purification at low temperatures using
a Nafion® 115 membrane using a hydrogen/nitro-
gen/carbon dioxide mixture. Testing was
performed at various temperatures and operating
pressures with hydrogen inlet compositions rang-
ing from 10 to 90 %. Detailed results from a 50 %
hydrogen mixture are shown in Fig. 24.9. Hydro-
gen purity was then measured as a function of
current density when testing was performed at
various temperatures (Fig. 24.10).
As expected, hydrogen purity increased with
increasing current density. Hydrogen purities of
>90 % were easily achieved at a wide range of
temperatures, pressures, and current densities.
Abdulla et al. [17] conducted an excellent and
detailed study on the efficiency of hydrogen
pumping using a Nafion® 115 membrane in
both a single stage and multistage design. Further
studies on perfluorosulfonic acid-based
membranes can be found in the additional
references [11, 18–21].

24.5.2 Poly(Ether Ether Ketone)-Based

24.5.1 Perfluorosulfonic Acid-Based
Membranes
Perfluorosulfonic acid-based membranes are
some of the most commonly studied membranes
in hydrogen pumping. Lee et al. [16] studied
Membranes
Poly(ether ether ketone)-based membranes
(PEEK) have also been studied in
low-temperature hydrogen pumping as more
cost effective alternatives to perfluorosulfonic
24 Electrochemical Hydrogen Pumping 535

Fig. 24.9 Polarization

curves for various cell
temperatures and pressures
(hydrogen inlet
composition 50 %)
Reproduced from [16] with
permission of Elsevier

Fig. 24.10 Hydrogen

purity vs. current density at
various cell temperatures
and operating pressures
(hydrogen inlet
composition 50 %).
Reproduced from [16] with
permission of Elsevier
536
Fig. 24.11 Current as a
function of applied
potential with varying
amounts of CO2 at 80  C
and 16 mL inlet.
Reproduced from [16] with
permission of the American
Chemical Society
acid-based membranes. Wu et al. [22]
synthesized a sulfonated PEEK (SPEEK) mem-
brane with a semi-interpenetrating network of
cross-linked polystyrene sulfonic acid (sIPN)
and performed hydrogen pumping tests. Current
was measured as a function of applied potential
at varying CO2 levels (Fig. 24.11). It can be seen
that the current quickly increases until the limit-
ing current is reached which was indicative of a
mass transport resistance. Polarization curves for
the sIPN membrane with various anode feeds can
be seen in Fig. 24.12 (active area 1.9 cm2).
24.6 Applications
The application of electrochemical hydrogen
pumping technology is relatively recent and has
been predominately limited to four areas:
(1) industrial hydrogen recycling, (2) fuel cell
applications (anode tail-gas recirculation for
reuse in fuel cells or related fuel cell systems),
(3) electroanalytical methods, and (4) hydrogen
compression. Of the four, only the first three
topic areas have seen significant development
efforts although electrochemical compression is
experiencing a higher degree of R&D activity
due to the current interest in hydrogen vehicle
K. Fishel et al.
refueling. Developed in the 1960s, the use of this
technology has been slow to emerge. This is
partly due to the fact that the EHP stack technol-
ogy parallels fuel cell development and commer-
cialization activities.
24.6.1 Electrochemical Industrial
Hydrogen Recycling
The recycling of hydrogen using electrochemical
methods in industrial applications has been a
recent focus of a number of companies, the
most predominant one being H2Pump LLC
(Latham, NY) [23]. In this application, hydrogen
is recovered from hydrogen-intensive industrial
processes, purified, and then made available for
reuse on-site. Applications include metallurgical
processes such as stainless steel annealing, braz-
ing, powder metal sintering, as well as semicon-
ductor production, to name a few. Chemical
processes that generate hydrogen are also
opportunities for this technology. There are a
number of challenges that must be overcome if
EHP methods are to be realized in industrial
settings. Regardless of the stack technology, it
must be scalable to be able to handle large
volumes of process gas, able to operate reliably
24 Electrochemical Hydrogen Pumping
Fig. 24.12 Polarization curve and Tafel Plots. Reproduced from [22] with permission of the American Chemical
Society
in the presence of a host of impurities from the
industrial process, and be able to generate
pressurized product hydrogen. The pressure
requirement to drive the “pumped” hydrogen
through a final clean up stage, typically a dryer,
as well as to feed it back into the feedstock mani-
fold of the site. As a result, a “system” to manage
the different unit operations is required as a func-
tion of the operating profile of a given applica-
tion. Such systems have been developed and
Fig. 24.13 shows a fully integrated unit that is
capable of pumping 100 kg of hydrogen per day.
24.6.2 Fuel Cell Applications
There are two potential uses of an EHP in com-
bination with fuel cells. In the first, anode tail-gas
recirculation, hydrogen is extracted from the fuel
537
cell stack anode exhaust. Once recovered, it is
then fed back to the original source of the hydro-
gen thereby improving the overall fuel efficiency
of the system. In the second, excess hydrogen
from the reformer is captured and recovered for
either recirculation or for use in other fuel cell
subsystems. In addition, recovered hydrogen
from either of these two sources within fuel cell
systems can be used for its heating or chemical
value, or for providing a source of hydrogen for
motive refueling needs. Hydrogen pumps have
been used by Bloom Energy Corporation to reach
technological and cost goals in planar solid oxide
fuel cells (PSOFC). In this application, a hydro-
gen pump can be used for hydrogen recycling or
external hydrogen delivery. The hydrogen pump
test duration lasted 2000 h and showed less than a
5 % performance degradation on hydrogen
production [24].
538
Fig. 24.13 H2Pump LLC hydrogen pumping unit
24.6.3 Electroanalytical Methods
With a strong emphasis on the development of
electrochemical membrane processes, e.g., water
electrolysis and fuel cells, electrode performance
must be well characterized electrochemically.
Use of a hydrogen pump concept can provide
insight into anode and/or cathode electrode elec-
trochemical characteristics. Furthermore, the
method can also be utilized to determine the
back diffusion of hydrogen through the mem-
brane [5, 25].
24.6.4 Compression
EHP technology is of interest as it can be used in
place of a mechanical compressor to generate
pressurized hydrogen. Although it is membrane
and hardware dependent, very high pressures
have been reported using EHP technology, at
least at the lab scale. The advantages include
(1) energy is consumed only to compress
K. Fishel et al.
hydrogen, (2) unlike a mechanical compressor,
a pressure head is not required, (3) the capital
costs of the core EHP system are lower than
mechanical methods, (4) high turn down ratio
characteristics, and (5) the energy requirements
are comparable to the mechanical compressor as
measured by the kW h kg1 of hydrogen which is
pumped and compressed. A significant develop-
ment challenge includes managing high differen-
tial pressures across the membrane, thereby
requiring sufficient mechanical strength of the
membrane separators, gaskets, and related stack
hardware. In addition, the forces encountered on
the end-plates of a stack can be significant. Due
to the logarithmic nature of the Nernst potential,
the energy requirements are approximately
6–10 kW h kg1, similar to that required by a
mechanical compressor. Pressures in the vicinity
of 345 bar have been recently reported [26] for
Nafion® membrane systems whereas 22 bar has
been reported for PBI high-temperature mem-
brane pumps [14].
24.6.5 Hydrogen Purification
Regardless of the source of the hydrogen, the
technique can be used for bulk purification of
hydrogen as long as the impurities that have to
be removed from the hydrogen do not impact the
electrochemical membrane process or the ancil-
lary subsystems.
24.6.6 Limitations of the Technology
There are a number of limitations of this technol-
ogy which also indicates opportunities for further
development. These are presented in Table 24.2.
24.6.7 Comparison to Fuel Cells:
Lifetime/MEA Stability
Although the electrochemical pump stack mod-
ule is similar to stacks used in membrane fuel
cells, there are significant differences. These
include the future prospect of not having to use
24 Electrochemical Hydrogen Pumping
Table 24.2 Technological limitations
Metric Impact
Performance Electrode stability
Membrane and electrode poisoning
Low anode hydrogen concentrations
Membrane flooding and/or drying
Pressure Membrane and hardware mechanical
limitation stability
Cost Utilization of precious metals
Membranes
precious metals, lower catalyst loadings, differ-
ent flow fields, the lack of oxygen in the cathode,
and low voltages for the hydrogen oxidation and
reduction processes. The latter two are of great
importance as the primary degradation mecha-
nism in low-temperature membrane fuel cells is
related to hydrogen peroxide radical attack of the
membrane and ionomer in the electrode layers.
The lack of oxygen in an EHP process creates
distinct lifetime and performance advantages
over fuel cells. Furthermore, as the voltages
required to “drive” the oxidation and reduction
reactions are by definition zero (except for a
small overvoltage), the carbon supports of the
catalysts are not at risk of oxidation.
24.7 Conclusions
High-temperature hydrogen separation using
PBI-based membranes has been demonstrated
to produce high purity hydrogen, even without
significant optimization of the cell design,
gasketing, and sealing strategies. A particular
advantage of high-temperature operation is the
increased tolerance to impurities that may be
present in reformation processes or in industrial
process streams. This is a critical aspect of high-
temperature EHP and expands the utility of such
devices for practical applications. Early work in
this field has confirmed the scalability of the
device to industrially relevant volumes with
power requirements that are considerably lower
than widely used existing technologies. Further
development of devices with higher purity gas
539
Consequences
Decreased performance and/or higher energy
requirements
Reliability
Catastrophic failure
Economics
production and higher pressures will be assisted
by additional hardware designs. It is expected
that longer lifetimes will be realized as compared
to fuel cells by the removal of the oxidative
degradation processes found in fuel cell
cathodes. There appear to be many opportunities
for membrane development, as well as, stack and
system designs that are tailored to meet the needs
of both current industrial and future hydrogen
markets.
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 Index

A B
Acid-base chemistry Binder
acid dissociation, 40, 42, 48 bipolar plate, 428–430
acid doping (doped), 47, 48, 51, 53 catalyst plastic pyramid, 429
acidity constant, 39 plastic pyramid, 429
base doping (doped), 48, 50, 54 thermoplastic, 428
chemical shift (NMR), 45 thermosetting, 522
Grotthuss mechanism, 37–39, 43, 46–48, 53 Bipolar plates
hydrogen bond, 37–39, 44, 45, 47, 48, acid uptake, 434–437
50, 53 binder, 428–430
hydrogen bond donor (acceptor), 38, 40, function, 426, 427
42, 43 gold coated, 502
ionic liquid, 39, 40, 44, 46, 47 graphite composite, 426, 433
ionicity, 39, 42–45, 47, 53 manufacturing, 428–430
polarizability, 42, 43 requirements, 427
protic, 42–47 stainless steels, 502
proton transfer, 37–40, 42, 44–48, 50, 53 Blends
vehicle mechanism, 37, 53 acid-base concept, 59–87
Walden rule, 46, 47 acid-excess, 50, 74
Acid doping base excess, 62, 63, 65, 86, 491
acid-base, 47, 48, 50 covalent cross-linking, 60, 79, 82
acid doping levels, 112–116, 122, Fenton test, 67, 95, 208
130, 152, 159, 160, 162, 200, 206, ionic cross-linking, 161
210, 220, 221, 223, 226, 228, 229, phosphoric acid uptake, 6
233, 239, 240, 243, 244, 262, thermal stability, 75, 76
268, 292, 337, 347, 391, 495,
503, 529, 533 C
adsorption isotherms, 184–186 Carbon
adsorption model, 179–183 bipolar plate, 320, 347, 426, 428
affinity, 198 catalyst support, 309
equilibrium, 113–116 composite membrane, 290, 291
hydration, 114 corrosion current, 305
hydrogen bond, 113 nanotubes, 74, 118, 290, 291, 430, 431, 501
level, 59, 63 potential dependence, 496
modified BET-isotherm, 180–183 protocols, 382, 501
Raman spectroscopy, 186–190 stabilized carbon, 307
swelling, 67, 159, 328 startup-shutdown, 382
Acid loss support, 27, 306, 307, 309, 310, 319, 334, 338,
evaporation, 345, 347 339, 341, 347–349, 361, 362, 379, 381, 395,
leaching, 339, 347 496, 498–500, 502, 504, 505, 539
vapor pressure, 340 synthetic graphites, 428, 430, 436, 437, 500
Area-specific resistance (ASR), 133, 503 Carbon monoxide
Auxiliary power unit (APU), 331, 333, 341, coverage, 304, 399
427, 428, 430, 488, 505 poisoning, 152, 235, 365, 390–392, 465, 504

# Springer International Publishing Switzerland 2016 541

Q. Li et al. (eds.), High Temperature Polymer Electrolyte Membrane Fuel Cells,
DOI 10.1007/978-3-319-17082-4
542 Index

Catalyst. See also Platinum catalyst Corrosion, 302–306, 319, 498–500

agglomeration, 495 carbon, 302–306, 319
alloys, 297, 306, 307, 310, 333, 342, 349 Cross-linking
coalescence, 496 covalent, 60, 62, 74–76, 79, 82–84, 104, 106, 107, 119
CO stripping, 300–302, 500 ionic, 60, 62, 63, 65, 67–69, 73–76, 79, 84, 86
degradation, 338, 340, 344, 349, 381, 495, 496
electrochemical surface area (ECSA), 298, D
310, 335, 338, 349, 501 Direct methanol fuel cell (DMFC), 142, 251, 291, 318
hydrogen underpotential deposition, 300 methanol crossover, 252
loading, 239, 297, 318, 337, 358, 362, Doping
373, 390, 499, 531, 539 acid, 4, 67, 92, 97, 99, 107, 111–113, 162,
migration, 496 220, 228, 261, 284, 291, 328, 490, 503, 533
nanoparticles, 495, 496 acid doping level, 59, 63, 112–116, 122, 132,
platinum, 2, 190, 342, 362, 401, 409, 152, 159, 160, 162, 200, 206, 220, 221,
499, 500, 529, 531 224, 226, 228, 229, 233, 239, 240, 243,
Catalyst binder 244, 262, 292, 337, 347, 391, 494, 495,
AB-PBI, 197 503, 529, 533
polyvinylidene fluoride (PVDF), 335, 429, acid uptake, 106, 113, 131, 196
434, 436, 437 adsorption isotherms, 183–187, 189
poly(2,5-benzimidazole) (AB-PBI), 334–336 amphoteric, 198
polytetrafluoroethylene (PTFE), 335 base, 62, 86
Catalyst degradation base doping level, 50
acid loss, 339, 340 conductivity, 240
carbon corrosion, 498–500 degradation, 240
dissolution rates, 497, 498 phosphoric acid, 28, 48, 51, 92, 97, 109,
electrochemical surface area (ECSA), 501 120, 151, 169, 189, 190, 195, 196, 200,
Ostwald ripening (mechanism), 497 202, 207, 209, 227, 230, 262, 263, 268,
redistribution, 495 275, 278, 285, 291, 292, 328, 333, 347,
sintering, 487 354, 361, 362, 391, 434, 490, 495, 505, 529
solubility, 497 Durability
Catalyst layer acid loss, 209, 340
design, 342–344 beginning of life, 487
hydrophilic, 347 degradation rates, 203, 235, 333, 379, 381,
hydrophobic, 318, 335, 336 502, 505
ionomer, 29 end of life (EOL)
Composite membranes long-term, 487
clay, 277 impurity effect, 504
coupling agent, 259, 260 post-mortem, 366–367
fillers, 6–20 startup-shutdown, 504, 505
lithium chloride, 261 steady state, 118, 122, 381, 502
Nafion/PTFE, 251, 252 target, 331–333, 337, 341, 488
PBI/PTFE, 259–261, 263, 266 thinning, 487, 489, 499, 505
poly(vinyl alcohol) (PVA), 252 Dynamic lifetime test
porous film, 252, 268, 269 loading cycling, 503
porous polytetrafluoroethylene (PTFE), 251–271 protocols, 504
reinforcement, 253–255, 257, 259 startup-shutdown, 503
silica, 246, 248
Conductivity E
activation energy, 135 Electrochemical hydrogen pumping
definitions and equations, 132, 133 compression, 538
four probe, 133, 134 effect of humidity, 530
in-plane, 432–434 hydrogen purity, 534, 535, 538
measurements, 133–135 lifetime, 538, 539
mixed, 133, 134 perfluorosulfonic acid, 534
Pouillet’s law, 133 polybenzimidazoles, 528, 529
temperature dependence, 135 poly(ether ether ketone), 534
through-plane, 434 Electrochemical impedance spectroscopy
Copolymers, 93–100, 102–105, 107, 109, 112, diagnostics, 389
114–116, 119 Nyquist plots, 135, 357, 479
Index 543

Electrochemical methods M
cyclic voltammetry (CV), 361–363 MEA
linear sweep voltammetry (LSV), 360 Mechanical properties
Electro-osmotic drag, 140–144 ASTM standard, 137, 438
water, 2, 144, 206–207 comparession, 138
creep, 138
F dynamic mechanical analysis (DMA), 139, 140
Fenton test. See also Oxidative stability elongation, 137
Fenton agent, 490, 505 hardness shore A, 438
ferrous ions, 95, 203, 490 indentation, 138
hydrogen peroxide, 102, 146, 202, 490 tear strength, 438
Fuel cell tensile stress, 137
activation loss, 358 Young´s (Elastic) modulus, 137
blends, 86 Membrane
compression, 138, 538 casting, 153, 197, 201, 203, 208
durability, 162, 209–210, 276 conductivity, 10, 205, 282, 284, 285, 347, 390, 391,
IR-correction, 356 396, 397, 481
mass transport, 356 crossover, 360, 399
ohmic loss, 356 degradation, 72, 209, 338, 340, 488
open circuit voltage, 141, 251, 292 doping, 327, 398
polarization curves, 7, 355, 356, 478, 483 gas diffusivity, 207
Tafel plot, 537 mechanical, 60, 221, 268
test procedure, 222, 229, 365 Membrane electrode assembly (MEA), 26, 27, 29–35, 69,
Fuels 87, 91, 109, 117, 118, 120–123, 128, 197, 203,
dimethyl ether, 514, 515 233–236, 251, 263–266, 268, 276, 297, 298, 308,
hydrogen, 2, 459, 537 309, 311, 315–324, 326–328, 332–349, 388, 392,
methane, 391, 514 397, 398, 401, 407, 409, 413, 414, 425–427, 436,
methanol, 459, 462, 465 437, 441, 442, 446, 448, 450, 451, 457, 465,
on-board, 515 467–469, 478, 489, 492, 494, 495, 497, 504, 505,
reforming, 459, 468, 477, 514 520, 529, 532, 538–539
accelerated stress test (AST), 380
G Butler–Volmer equation, 355
Gas diffusion compression (contact pressure), 367–378
electrode, 134, 208, 262, 320, 322, 323, 388, EIS, 357–360, 364
392, 394–396, 411 long-term test, 378
gas diffusion layer (GDL), 209, 233, 275, 311, ohmic resistance, 27, 31, 34, 297, 338, 342,
315–317, 320, 323, 324, 332, 353, 354, 346, 349, 368
391, 392, 396, 403, 426, 434, 493, 502, 505 open circuit voltage, 30, 33, 265, 504
permeability, 207 structure design, 341–345, 347, 348
Gasket Tafel slope, 333, 336
elastomer, 427, 438 Membrane modifications
function, 426 composites, 196, 207–209
plastic pyramid, 429 crosslinking, 196, 208–209
requirement, 427 grafting, 208
Grotthus mechanism, 48, 290 Methanol
combustion heating, 462, 469–471
H cross-over, 6, 11, 18, 35
Homopolymer, 92–94, 96 oxidation, 6, 143
Hydrocarbon membranes permeation, 143, 144
sulfonated, 11–14, 16–18 reformers, 91, 123, 459–462, 464, 467, 469,
Hydrogen bond(ing), 37–39, 44, 45, 47, 48, 50, 53, 113, 474–476, 514–518
138, 228, 239, 253, 254, 256, 258, 259, 348 Molecular weight
Hydrogen evolution reaction (HER), 300, 311 gel permeation chromatography, (see also Size
Hydrogen oxidation reaction (HOR), 297, 298, exclusion chromatography (SEC)), 66, 67,
303, 304, 310, 311, 532, 533 69, 73, 95, 130
light scattering, 127–129
I Mark–Houwink–Sakurada, 154, 241
Ionicity, 39, 42–45, 47, 53 single-point method, 154
Ionic liquid, 39, 40, 44, 46, 47, 286 viscosity, 128–129
544 Index

O dissolution, 320, 487, 488, 495, 496, 498, 505

Oxidative degradation migration, 345
chain scission, 490 nanoparticles, 297, 334, 338, 497, 505
Fenton agent, 489 ostwald ripening, 298
peroxide radicals, 489 redistribution, 308
phosphoric acid, 505 Polyacid membranes, 51
thermal, 489 Polybenzimidazole
weight loss, 490 membrane fabrication, 156
Oxidative stability, 66, 80, 94–96, 100, 102, 107, 121, solubility, 195
144–147, 489, 490 Polybenzimidazole blends
Oxygen reduction reaction (ORR) acid–base, 490
acid adsorption, 300, 333 acidic polymers, 62
catalyst, 303, 333, 334 chemical stability, 60
kinetics, 297, 303, 333, 342 conductivity, 60, 217, 290, 491
mechanism, 336 doping, 28, 48, 170, 204, 205
oxygen solubility, 404 thermal stability, 66, 202
Polybenzimidazole membranes
P acid doping, 239
Perfluorosulfonic acid chemical stability, 67, 286
composite, 6–23 conductivity, 217, 290, 491
inorganic fillers, 6 electro-osmotic drag, 140
modified, 23–27, 35 gas permeability, 141, 146, 347
phosphoric acid doping, 328 gas solubility, 141, 390
short side chain, 18, 27–34 mechanical strength, 203, 207
Permeability structure and morphology, 201
gas, 140–141, 146, 196, 207, 239, 336, 347, 369 thermal stability, 202
hydrogen, 141–142, 207, 209 Polybenzimidazole modification
hydrogen stripping, 142 blend, 6, 74, 95
oxygen, 141 composite, 60, 246, 248, 277, 279, 282,
Phosphoric acid 290–292
acid–base chemistry, 3, 37–54 crosslinking, 267
acidity, 51, 171, 179 grafting, 62
acid retention, 276 hybrid, 284
anhydride, 135, 170 N-substitution, 161, 208
conductivity, 170, 174–175, 190, 204, 205 pendant groups, 201
evaporation, 116, 494 Polybenzimidazole solutions
fuel cell (PAFC), 2, 4, 169, 179, 268, 318–320, conformation, 255
322, 327, 328, 333, 335, 336, 344, 345, 348, filtration, 136
388, 389, 396–403, 414, 495, 497, 505, 529 lithium chloride, 253
leaching, 248, 249 radius of gyration, 255–257
protolytic equilibria, 171–173 solubility, 128
vapour pressure, 173–174 static light scattering, 255, 256
viscosity, 175–176 viscosity, 254
Walden plot, 179 Polybenzimidazole synthesis
Phosphoric acid fuel cell (PAFC), 492 degree of polymerization, 127
Platinum alloys main chain modifications, 156
core-shell, 342 microwave assisted synthesis, 154
Pt-Al, 333 molecular weights, 127, 128, 152,
Pt-Co, 334, 342, 349 154, 155
Pt-Cr, 333, 342 polymer repeat unit, 59, 195
Pt-Fe, 333 solubility, 128, 223
Pt-Ni, 333, 342, 349 solvent free, 152
Pt-Ru, 333 tailored basicity, 242
Pt-V, 333 Polymer
Platinum catalysts decomposition temperature, 111, 208
agglomeration, 318, 338, 339, 341, 344, 345, glass transition temperature, 27, 29
347, 349 homopolymer, 224, 230, 233
carbon corrosion, 498, 505 molecular weight distribution (MWD), 490
coalescence, 345 stability, 492
Index 545

Polyphosphoric acid (PPA) thermal, 3, 14, 44, 60, 65, 66, 69, 71, 75, 86, 93, 95,
content, 115 98, 99, 103–105, 144, 151, 152, 160, 162, 200,
copolymers, 230 202–203, 239, 241, 276, 278, 284, 286, 287,
PBI variants, 156 291, 336, 428, 431
phosphoric acid contents, 132, 138, 195, 200, 203, Stacks
207, 208, 219, 337, 340, 341, 349, 405, 502 air-Cool, 452, 456, 460
polyphosphoric acid process, 529 construction materials, 450
solvent, 153, 196, 217 design, 441, 447, 449, 455, 460, 521
Protic ionic liquid, 44, 46, 47 Sulfonated PBI, 131
Proton conductivity Swelling
acid-base, 37–54 acid doping, 67
Grotthuss mechanism, 38, 206 linear, 132
hydrogen bonds, 40–43 van der Waals volume, 67
permanent, 239, 240 volume, 65, 67, 200, 208, 503
proton transfer, 37, 48 water uptake, 198, 328
vehicle mechanism, 29 System diagnostics
Pyridine containing polymers air-cooled, 460–462
acid uptake, 111 CO effect, 2, 390, 532
aromatic polyethers, 62, 91–123 CO2 effect, 2, 532
cross-linked, 72, 104–111 efficiency, 468, 475
fuel cells, 91, 95, 96, 117, 119, 122 impedance, 465, 466, 481
membrane electrode assembly, 128 liquid cooled systems, 462–465
side group functionalized, 96–104 system control, 463
synthesis, 91–96 system idling, 483
water uptake, 131
R
Relative humidity T
control, 147–148 Targets
definition, 147–148 bipolar plate, 426, 427
dew point method, 147 catalyst loading, 337
mechanical properties, 33, 67, 113 catalyst support, 334
proton conductivity, 243, 244, 279, 284 cost, 331, 332
DOE, 505
S durability, 333
Simulation gasket, 426, 427
Monte Carlo method, 344 membrane, 276
polymer chain, 219 Thermal stability
three-dimentional kinetic, 338 differential (DTA), 65, 71
Size exclusion chromatography (SEC), 130–131 thermogravimetric analysis (TGA), 60, 71, 75, 76, 79
Sol-gel method
PPA process, 217, 218 V
SiO2 fillers, 25 Viscosity
Solid acid, 53 dynamic shear viscosity, 255, 256
Solubility elastomer, 438
hydrogen, 399, 404 helix test, 438
methanol, 141 inherent, 129, 152, 197, 203, 204, 217, 219–221,
Solvents 231, 242, 529
dimethylsulfoxide (DMSO), 98 intrinsic, 128, 129, 154, 197, 241, 242, 254
methanesulfonic acid (MSA), 196 Mark-Houwink equation, 203, 241
N,N-dimethylacetamide (DMAc), 136, 156 PBI, 254
N,N-dimethylformamide (DMF), 156, 196 specific, 128, 154
N-methyl-2-pyrrolidone (NMP), 136, 156, 196
Stability W
oxidative, 66, 80, 94–96, 100, 102, 107, 121, Walden plot, 44, 46, 47
144–147, 489, 490 Walden rule, 46
PBI, 67, 286, 287 Water uptake, 15, 199