ECS Trans.-2013-Ayers-121-30

ECS Transactions, 45 (23) 121-130 (2013)
10.1149/04523.0121ecst ©The Electrochemical Society
Characterization of Anion Exchange Membrane Technology for

Low Cost Electrolysis
K.E. Ayersa, E.B. Andersona, C.B. Capuanoa, M. Niedzweickia, M. Hicknerb,

C-Y Wangb,c, Y. Lenc, and W. Zhoub
a
Proton OnSite 10 Technology Drive, Wallingford, CT 06492, USA
b
Department of Material Science & Engineering,
c
Electrochemical Engine Center, Department of Mechanical and Nuclear Engineering,
Pennsylvania State University, University Park, PA 16802, USA
Proton OnSite’s line of commercial products based on proton

exchange membrane (PEM) technology is competitive with
delivered hydrogen in many industrial gas markets. Proton has
demonstrated significant efficiency improvements and cost
reductions over the past several years. Still, major advances are
required in order to provide a cost-competitive hydrogen source for
energy markets. Alkaline exchange membranes (AEMs) offer a
potential long term pathway to lower cost electrolysis because they
can operate at the high current density and high differential
pressure of the PEM while using non-precious metal catalysts and
base metal cell materials for low cost. Proton is currently
performing on an ARPA-E project in collaboration with Penn State
to develop an AEM-based regenerative fuel cell. This paper
describes progress to date on the AEM electrolyzer being
developed under this effort.
Introduction
Water electrolysis has benefits over other hydrogen generation technologies due to
the lack of carbon footprint when integrated with a renewable source of energy.
Specifically, ion exchange membrane-based electrolysis is a promising technology for
hydrogen generation applications because of the lack of corrosive electrolytes, small
footprint, and ability to generate at high pressure, requiring only deionized water and an
energy source. While Proton believes that the PEM systems have significant opportunity
for both capital and lifecycle cost through cost reduction and efficiency improvements, an
anion exchange membrane-based system would enable both the advantages of the PEM
and the alkaline liquid based systems. However, anion exchange membrane technology
is much less mature than PEM technology, and the polymers have not been as stable.
Status of the Technology
Proton exchange membrane (PEM) electrolysis has been known for over 50 years,
starting from GE technology. Proton OnSite is currently the world leader in
manufacturing of PEM hydrogen generation products using electrolysis, with over 1800
units in the field. Pure hydrogen is used in a variety of industrial applications, including
acting as a cooling fluid for power plant turbine generators, a reducing atmosphere for
heat treating and semiconductor processing, and as a carrier gas for spectroscopic
121
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applications such as gas chromatography. Proton’s on site hydrogen generators are cost
competitive with delivered hydrogen for these applications. However, interest in
hydrogen for energy applications has increased the need to decrease capital cost and
increase efficiency of electrolysis and other generation methods.
PEM versus Alkaline
There are two main types of low temperature electrolysis currently commercially
available. Alkaline electrolysis uses liquid electrolyte, with high concentrations of
potassium hydroxide to provide ionic conductivity and to participate in the
electrochemical reactions. PEM electrolysis replaces the liquid electrolyte with a solid
polymer electrolyte, which selectively conducts positive ions such as protons. The
protons participate in the water-splitting reaction instead of hydroxide, creating a locally
acidic environment in the cell.
There are advantages and disadvantages of each system. One advantage of KOH
electrolyzers is the stability of nickel and stainless steel in this environment, enabling
elimination of expensive materials of construction. However, in the KOH system, the cell
construction results in a low bubble point between the oxygen and hydrogen cavities,
requiring balanced pressure operation. This limitation requires controlled shutdown
procedures to maintain low hydrogen concentration in the oxygen compartment in order
to ensure safe operation. This configuration also requires the use of high pressure oxygen,
which adds stringent cleanliness specifications for safety reasons as well as high pressure
plumbing on the oxygen-water fluids loop. The KOH electrolyte is highly corrosive,
adding additional complexity to the balance of plant as well as monitoring of
concentration to determine electrolyte replacement needs. Alkaline electrolysis is also not
as efficient as PEM, limiting use to fairly low current densities. The ideal solution is an
alkaline-based ion exchange membrane that gives the benefits of the solid polymer
electrolyte technology with the materials compatibility of liquid alkaline system.
Proton believes there are multiple development pathways towards low cost hydrogen
production using membrane-based electrolysis and is actively pursuing both acid and
alkaline technology development strategies. The commercially-mature PEM electrolysis
platform offers near term cost reduction and efficiency improvement opportunities by
leveraging its high current density capability (reduced stack capital cost) and benefiting
from advanced materials development (ultra-low loading catalyst structures, advanced
membranes and catalysts, and low cost bipolar plate materials and coatings) being
conducted for the PEM fuel cell. This contrasts with the early-stage AEM technology
where the focus is on membrane and catalyst development to establish a stable, reliable
architecture upon which further innovation can then take place. The use of non-noble
metal materials to reduce cost will ideally enable operating design points at lower current
densities, which will create an added benefit of improved efficiency.
The AEM Concept
The reaction scheme for the AEM electrolysis cell is shown schematically in Figure 1.
In AEM electrolysis, water is reacted at the cathode electrode through the addition of
electrons, dissociating into hydrogen and hydroxide ions. The hydroxide ions carry the
charge through the anion exchange membrane to the anode side of the cell where they
122
then recombine to produce oxygen and water. The half cell reactions for the AEM
electrolysis cell are shown below. It is important to note that the anode reaction potential
is only 0.4V. This low voltage enables the use of less noble materials which can
substantially reduce the material cost of the cell.
Anode: 4OH- → O2 + 2H2O + 2e- Eo = 0.4V [1]
Cathode: 2H2O + 2e- → 2H2 + 4OH- Eo = -0.83V [2]
Full: 2H2O → 2H2 + O2 Eo = 1.23V [3]
For comparison, the corresponding PEM electrolysis reaction based on acid chemistry
is also shown. The major difference between the AEM and PEM electrolysis cell,
beyond the ion conductor itself, is that water is reacted at the opposite side of the cell.
This is also where hydrogen is produced. This characteristic creates implications
regarding the complexity of the system configuration for water feed, product hydrogen
removal and thermal management.
4e- 4e-
O2 + 4H+ 2H2 O2 + 2H2O 2H2 + 4OH-
Anode H+ Cathode Anode OH- 2e- Cathode
2H2O 4H+ 4OH- 2H2O
Acid Alkaline
Figure 1. Comparison of electrode reactions for acid-based proton exchange membrane
(PEM) and alkaline exchange membrane (AEM) electrolysis.
As mentioned above, due to the low operating potentials, the AEM electrolysis
pathway enables the use of the nickel and cobalt-based catalysts currently used in
alkaline electrolyte systems, as well as stainless steel flow fields, while maintaining the
advantages of the PEM system of high differential pressure operation, pure water as the
carrier fluid, and inexpensive system component materials. A comparison of the raw
material costs for catalysts and flow fields is presented in Figure 2, based on data from
published prices on the American Metals Markets. Note that the y-axis represents a
logarithmic scale.
As seen in the figure, replacing the noble metals typically found in PEM electrolysis
stacks with metals typically found in liquid alkaline electrolyzers, such as nickel, should
reduce the raw material cost of the catalyst precursors by orders of magnitude. Similarly,
moving to stainless steel based bipolar plates or flow fields should substantially reduce
the raw material cost vs. typical materials used today in PEM systems, such as titanium.
123
Stainless steel is also less difficult to machine or form than titanium, which should result
in decreased processing costs.
$100,000
$10,000
Raw Material $/lb

$1,000
$100
$10
$1
Platinum Iridium Nickel Titanium Stainless
Catalyst Flow fields

Material
Figure 2. Comparison of raw material costs for AEM and PEM electrolysis.
AEM Materials Development
There is a critical need for new materials in order to make the AEM electrolysis
technology robust and commercially viable. The high priority development activities are
primarily associated with new anion exchange membranes and high activity non-noble
metal catalysts. In addition, integration of promising catalysts and membranes together
into highly functioning membrane-electrode-assemblies (MEAs) is also a critical need.
Activities at Proton addressing these development areas are described in the next several
sections.
Membrane Development. Anion exchange membranes have many physical properties

that make them attractive for application in electrolysis. One such property is gas
permeation. In Figure 3, gas cross-over is compared for a commercial AEM versus a
Nafion® PEM from DuPont, as a function of applied differential pressure at elevated
temperature. The AEM exhibits over a factor of five reduction in cross-over at up to
2000 psi differential pressure as compared to the PEM.
In addition to gas cross-over, mechanical properties of several AEM candidates

prepared by Penn State were compared to commercial PEM and AEM membranes.
Figure 4 presents a comparison of mechanical strength and ductility measurements for the
membrane samples. The results highlight the potential advantages of the Penn St.
membranes versus either the commercial PEM or AEM materials in terms of mechanical
strength, which is an important consideration in sealing. However, depending on the
material formulation, the properties can vary widely and therefore present opportunities
for optimization to give an AEM that can have both high strength and ductility.
124
Normalized Nitrogen Permeation Rate, 80 oC

25
5 mil Nafion
Tokuyama
Commercial
20
15
10
0
0 500 1000 1500 2000 2500
Pressure (psi)
Figure 3. Comparison of gas cross-over for PEM and AEM membranes as a function of
differential pressure.
AEM baseline
AEM baseline
AEM baseline
Figure 4. Comparison of various mechanical properties for PEM and AEM membranes.
Stability of the AEM in an operating electrolyzer environment is also a key issue.

Hydroxide is a very aggressive oxidizing agent and hydroxide radical attack is a well
known degradation mechanism for ion exchange polymers. A simple degradation test for
hydroxide attack is exposure to Fenton’s reagent. A candidate Penn State AEM was
subjected to the Fenton’s test for up to 5 hours. FTIR and RAMAN spectroscopy were
used to monitor the stability of the polymer. The spectroscopy results are presented in
125
Figure 5 for 0, 2.5 and 5 hr exposure times. The AEM membrane was physically intact
after 5 hr exposure but from the spectra analysis there was a loss of signal attributed to
the SO2 peak as well as the C-O-C signal, indicating polymer degradation. Signal loss
associated with the C-N and HCO3- peaks was also observed. It is worth noting that the
Fenton’s test is considered an aggressive test and may not correlate to actual membrane
operating life. It should only be used to indicate relative stability. Nevertheless, survival
for 5 hours in this environment is a positive indication of long term stability.
Visual inspection of the candidate AEM subjected to the Fenton’s test was also
conducted using optical microscopy. Micrographs of membrane samples at 0, 2.5 and 5
hr exposure are presented in Figure 6. From the micrographs some surface cracking and
possible dissolution was noted, but overall membrane structure remained intact.
QARadel - 00 Hour QARadel - 00 Hour

QARadel - 2.5 Hour QARadel - 2.5 Hour
QARadel - 5.0 Hour QARadel - 5.0 Hour
Normalized Counts
Normalized Counts
600 800 1000 1200 1400 1600 1800 400 800 1200 1600
-1 -1
Wavenumber, cm Raman Shift, cm
Figure 5. FTIR (left) and RAMAN (right) spectrum for AEM membrane subjected to
Fenton’s test as a function of exposure time.
As prepared membrane 5x After 2.5 Hours Fenton 5x After 5.0 Hours Fenton 10x
Figure 6. Optical microscopy analysis of AEM membrane subjected to Fenton’s test as a

function of exposure time.
Stability of a candidate AEM prepared by Penn St. was also compared with a
commercially available AEM using the same Fenton’s test/spectrum analysis method.
Results are presented in Figure 7. Comparing the intensity of the primary quinone
absorbance peak (QA) at 974 cm-1 as a function of exposure time showed that the QA
126
group of the commercial AEM degraded faster than that of the Penn St. AEM at both 100
and 135°C test temperatures.
AEM MEA Development. In order to accurately assess the stability of the AEM, a
membrane-electrode-assembly (MEA) must be fabricated for operation in an actual
electrolysis cell. Processing of the AEM into an MEA has its own set of development
challenges. PEM electrolysis MEA preparation methods are well developed and
understood. Also, standard ionomer solutions and binders exist in order to create
optimum electrode structures and integrate them on the membrane. The AEM has a
limited processing temperature range requiring development of milder conditions for
electrode attachment. Available options of solubilized anion exchange ionomer used in
ink electrode formulation is also limited, requiring further experimentation.
AS-4 135 C 135 C

Commercial
1.0 Commercial
AS-4 100 C 100 C
R-AEM 135 C
Normalized absorbance (a.u.)
R-AEM 100 C
0.8
0.6
0.4
0.2
0.0
0 2 4 6 8 10 12
Time (h)
Figure 7. Comparison of the quinone absorbance peak (QA) at 974 cm-1 for two different
AEM polymers as a function of exposure time and temperature in a Fenton’s degradation
test.
Given these limitations, Proton has made steady progress in AEM electrolyzer MEA
development since 2010. Figure 8 presents a progression of single cell AEM electrolysis
polarization curves over time to illustrate the effect of these MEA process improvements.
At the target current density of 500 mA/cm2, a reduction in cell potential of over 700 mV
has been achieved, approaching target of 1.8V. More recent progress has actually
generated results that exceed this target. With steady progress in the development of a
high performance AEM electrolysis MEA, current work is focusing on further membrane
improvements as well as the development and integration of high activity, non-precious
metal catalysts to reduce the unit cell cost.
127
2.9
2.8
Performance progression
2.7
with process improvements
2.6
Operating Potential (V) Dec-10
2.5
Jan-11
2.4
2.3 Aug-11
2.2 Aug-11
2.1
Sep-11
2
1.9
1.8
1.7
Target Potential 1.8 V @ 500 mA/cm2
1.6
1.5
0 100 200 300 400 500 600 700 800 900 1000
Current Density (mA/cm2)
Figure 8. Impact of MEA process improvements on overall single cell operating

performance for an AEM electrolysis cell.
Non-Precious Metal MEAs. As previously discussed, a major potential advantage of

AEM electrolysis versus PEM electrolysis is the ability to use non-platinum group metal
(PGM) catalysts. The impact of substituting non-PGM catalysts in presented in Figure 9.
Current-voltage polarization data is presented for several AEM electrolysis single cells
with varying PGM contents. The lower polarization curves represent the baseline cell
performance for several MEAs, all using PGM catalyst on both the anode and cathode
side of the cell. Substituting non-PGM oxygen evolution catalyst at the anode results in a
modest increase in cell potential of approximately 0.3V across a broad operating current
density range. Replacing the PGM catalyst at both electrodes results in a further increase
in cell potential.
Clearly, the use of a non-PGM cathode catalyst for hydrogen evolution has a greater
negative impact on cell performance than on the anode side of the cell, and both catalysts
still need development to reach equivalency with the current PGM catalysts being used.
This catalyst development is ongoing and some results from Northeastern University
investigating the use of ternary catalysts is presented in Figure 10. Early indications are
that ternary catalyst combinations show enhanced activity versus the binary systems and
all exceed the noble metal-based baseline anode catalyst performance. More work is
needed to identify a stable catalyst support and also scale the synthesis to reasonable
quantities for multi-cell stack evaluation.
128
No precious metal
2.7 No precious metal on anode
New baseline
New baseline
2.5 Previous Benchmark
Operating Potential (V)

2.3
2.1
1.9
1.7
1.5
0 100 200 300 400 500 600 700 800 900 1000
Current Density, (mA/cm2)
Figure 9. Effect of non-PGM based catalyst on single cell AEM electrolyzer
performance.
Figure 10. Chrono-amperometric characterization of advanced non-PGM oxygen

evolution catalysts for use in AEM electrolysis cells (courtesy of Northeastern Univ.).
Summary
The pathway to lower cost hydrogen generation by membrane electrolysis can be

viewed as a continuum, where near-term material and design advances can significantly
reduce the cost of PEM electrolysis and parallel developments in AEM electrolysis
materials can extend this cost reduction progression in the long term (Figure 11). Proton
believes that alkaline exchange membranes show promise in the long term for hydrogen
generation applications. To date, Proton has shown that AEM electrolysis performance
can reach levels that are needed for commercial viability. Durability and reliability of
these materials still remain an issue and area for further development. Proton is
continuing to pursue parallel approaches in membrane materials and catalysts through
collaboration with university and industrial partners. Due to the broad interest in these
materials for fuel cell applications, multiple research groups are investigating new classes
of materials that may have utility in electrolysis as well. As a commercial manufacturer
and supplier of hydrogen generation systems based on polymer electrolyte membranes,
Proton can provide real world testing the AEM technology, with the goal of validating its
utility in the future hydrogen energy markets.
129
100%
90% PEM Alkaline

80% Projected PEM
progression
70%
Materials only
60%
% Baseline
Materials and labor

50%
40%
30%
20%
10%
0%
Figure 10. Projected electrolysis cell cost projection for both PEM and AEM technology
development.
Acknowledgments
Authors gratefully acknowledge financial support from the ARPA-E GRIDS program
for the work discussed in this paper. The authors also acknowledge the valuable
contributions from Dr. Sanjeev Mukerjee and Michael Bates at Northeastern University.
130

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ECS Transactions, 45 (23) 121-130 (2013)

10.1149/04523.0121ecst ©The Electrochemical Society

Characterization of Anion Exchange Membrane Technology for

K.E. Ayersa, E.B. Andersona, C.B. Capuanoa, M. Niedzweickia, M. Hicknerb,

Proton OnSite’s line of commercial products based on proton

Status of the Technology

PEM versus Alkaline

The AEM Concept

Anode: 4OH- → O2 + 2H2O + 2e- Eo = 0.4V [1]

Cathode: 2H2O + 2e- → 2H2 + 4OH- Eo = -0.83V [2]

Full: 2H2O → 2H2 + O2 Eo = 1.23V [3]

O2 + 4H+ 2H2 O2 + 2H2O 2H2 + 4OH-

Anode H+ Cathode Anode OH- 2e- Cathode

2H2O 4H+ 4OH- 2H2O

Raw Material $/lb

Catalyst Flow fields

AEM Materials Development

Membrane Development. Anion exchange membranes have many physical properties

In addition to gas cross-over, mechanical properties of several AEM candidates

Normalized Nitrogen Permeation Rate, 80 oC

Stability of the AEM in an operating electrolyzer environment is also a key issue.

QARadel - 00 Hour QARadel - 00 Hour

Figure 6. Optical microscopy analysis of AEM membrane subjected to Fenton’s test as a

AS-4 135 C 135 C

Current Density (mA/cm2)

Figure 8. Impact of MEA process improvements on overall single cell operating

Non-Precious Metal MEAs. As previously discussed, a major potential advantage of

Operating Potential (V)

Figure 10. Chrono-amperometric characterization of advanced non-PGM oxygen

The pathway to lower cost hydrogen generation by membrane electrolysis can be

90% PEM Alkaline

Materials and labor

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