ARTICLES

PUBLISHED: 22 AUGUST 2016 | ARTICLE NUMBER: 16120 | DOI: 10.1038/NENERGY.2016.120

An operationally flexible fuel cell based on

quaternary ammonium-biphosphate ion pairs
Kwan-Soo Lee1†, Jacob S. Spendelow1, Yoong-Kee Choe2, Cy Fujimoto3 and Yu Seung Kim1*

Fuel cells are promising devices for clean power generation in a variety of economically and environmentally significant
applications. Low-temperature proton exchange membrane (PEM) fuel cells utilizing Nafion require a high level of hydration,
which limits the operating temperature to less than 100 ◦ C. In contrast, high-temperature PEM fuel cells utilizing phosphoric
acid-doped polybenzimidazole can operate effectively up to 180 ◦ C; however, these devices degrade when exposed to water
below 140 ◦ C. Here we present a different class of PEM fuel cells based on quaternary ammonium-biphosphate ion pairs that
can operate under conditions unattainable with existing fuel cell technologies. These fuel cells exhibit stable performance
at 80–160 ◦ C with a conductivity decay rate more than three orders of magnitude lower than that of a commercial high-
temperature PEM fuel cell. By increasing the operational flexibility, this class of fuel cell can simplify the requirements for
heat and water management, and potentially reduce the costs associated with the existing fully functional fuel cell systems.

B
y using hydrogen produced from renewable energy sources,
such as solar and wind, fuel cells can provide carbon-neutral
power without any pollutants, such as SOx and NOx 1 . Initial
commercialization of clean, high-efficiency fuel cell electric vehicles
is already underway2 , but further technological innovation is needed
to improve the cost competitiveness of fuel cells in the marketplace3 .
Low-temperature PEM fuel cells that use Nafion are at present
being commercialized in fuel cell vehicles, but these cells can
operate only at relatively low temperatures and high hydration
levels4 (Fig. 1a); therefore, they require humidified inlet streams and
large radiators to dissipate waste heat. High-temperature PEM fuel
cells that use phosphoric acid (PA)-doped polybenzimidazole (PBI)
could address these issues5 , but these PBI-based cells are difficult
to operate below 140 ◦ C without suffering loss of PA (ref. 6; Fig. 1b).
The limited operating temperature range makes them unsuitable for
automotive applications, where water condensation from frequent
cold start-ups and oxygen reduction reactions at the fuel cell cathode
occur during normal vehicle drive cycles.
In this work, we demonstrate that fuel cells based on
quaternary ammonium (QA)-biphosphate ion-pair-coordinated
polyphenylene (PA-doped QAPOH) PEMs can avoid the limitations
of Nafion and PBI-based fuel cells, enabling operation under a
wide range of conditions that are off-limits for existing fuel cell
technology. These PEMs can conduct protons through stable ionic
pair complexes and enable fuel cell operation at temperatures from
80 to 180 ◦ C (Fig. 1c).
Energetics of quaternary ammonium-biphosphate ion pairs
The operating temperature window of a PEM fuel cell is dictated
by the interactions between the acid (for example, tethered
sulfonic acid or free phosphoric acid) and the base moieties (for
example, free water or tethered QA) in the PEM. The hydrogen
bonding interactions between the sulfonic acid group and water
molecules in Nafion is only 15.4 kcal mol−1 (Fig. 1d), which does
not provide enough stability above the boiling temperature of
water, leading to membrane dehydration. For PA-doped PBI, a
proton from PA is located between the PA and benzimidazole,
but due to the weak basicity of benzimidazole, the proton
remains close to the biphosphate anion, producing a relatively
weak benzimidazole···H·H2 PO4 interaction. The intermolecular
interaction energy, E int , between benzimidazole and PA is computed
as 17.4 kcal mol−1 (Fig. 1e), which is only 4.8 kcal mol−1 greater than
that between PA and one water molecule, about 12.6 kcal mol−1 .
Additional PA molecules have even weaker interactions within
the matrix. Due to the relatively weak interaction, benzimidazole
tends to lose PA easily with water absorption. Consequently,
PA-doped PBI requires a high concentration of base moieties,
about >6 mmol g−1 , and a high acid content, about ∼90 wt%,
to impart sufficient anhydrous conductivity7,8 . For PA-doped
QAPOH, the relatively strong basicity of QA hydroxide causes
complete PA deprotonation, enabling a strong QA+ ··H2 PO4 −
interaction. The intermolecular interaction energy between
benzyltrimethylammonium (BTMA) and the biphosphate anion
is computed as 151.7 kcal mol−1 , which is 135.4 kcal mol−1 greater
than the interaction between biphosphate and one water molecule,
about 16.3 kcal mol−1 (Fig. 1f). The intermolecular interaction
energy between the ionic pair and PA would gradually decrease
when additional PA molecules are associated. Through the stronger
interactions driven by the ionic pair, PA-doped QAPOH maintains
a high PA content in spite of water absorption. Since the presence of
water increases the proton transfer rate9 , PA-doped QAPOH does
not require a high concentration of cationic groups.
Phosphoric acid retention
Table 1 compares the properties of PA-doped QAPOH and PA-
doped PBI. The concentration of base moiety in QAPOH is
1.7 mmol g−1 , approximately 3.8 times less than that in PBI. The
number of PA molecules per base moiety for PA-doped QAPOH
is 14.4, which is slightly greater than that for PA-doped PBI. This
result confirms that the interactions of PA in PA-doped QAPOH

1 MPA-11: Materials Synthesis and Integrated Devices, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA. 2 National Institute of

Advanced Industrial Science & Technology, Tsukuba 305-8568, Japan. 3 Organic Materials Science, Sandia National Laboratory, Albuquerque,
New Mexico 87185, USA. † Present address: C-CDE: Chemical Diagnostic and Engineering, Los Alamos National Laboratory, Los Alamos,
New Mexico 87545, USA. *e-mail: yskim@lanl.gov

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ARTICLES NATURE ENERGY DOI: 10.1038/NENERGY.2016.120

a 100 90 40 20 0 RH (%) d
1 Water−bisulfate
Nafion (hydrogen bonding)
PEM

Conductivity (S cm−1)
dehydration

0.10

Low Operating % RH scale

reaction temperature
kinetics 0 50 100
0.01
Eint = 15.4 kcal mol−1
20 40 60 80 100 120 140 160 180 200
Temperature (°C)

b 50 30 10 0 RH (%) e
1 Benzimidazole−PA
PA-doped PBI (acid−base interaction)
Conductivity (S cm−1)

0.10

PA Operating
0.01 leaching temperature

Eint = 17.4 kcal mol−1

20 40 60 80 100 120 140 160 180 200
Temperature (°C)

c 50 30 5 0 RH (%) f
1 BTMA−biphosphate
PA-doped QAPOH (ion pair interaction)
Conductivity (S cm−1)

0.10

Low Operating temperature

reaction
0.01 kinetics

Eint = 151.7 kcal mol−1

20 40 60 80 100 120 140 160 180 200
Temperature (°C)

Figure 1 | Operating temperature of PEM fuel cells and PEM interactions. a–c, Comparison of proton conductivity of Nafion (a), PA-doped PBI (b) and
PA-doped QAPOH (c) (Supplementary Fig. 1); the background colour in the plots indicates the relative humidity (RH) of the measured data points. Graphs
also show the fuel cell operating temperature and limitations; Nafion and PA-doped PBI data were obtained from refs 4,7, respectively. d–f, Intermolecular
interaction energy of water–bisulfate (d), benzimidazole–PA (e) and BTMA–biphosphate (f). The intermolecular interaction energy was calculated by
density functional theory employing the ωB97XD functional and 6-311++G(2d,2p) basis sets.

Table 1 | Property comparison between PA-doped QAPOH and PBI systems.

Polymer Concentration of base moiety Number of PA per base moiety Polymer content∗ Number of H2 O
(mmol g−1 ) (%)
Per base moiety Per PA (doped)
Undoped Doped
QAPOH 1.7 14.4 ± 0.1 29 27† 64 4.4
PBI 6.5 11.6 ± 0.1 12 3.2‡ 70 6.0
∗
For dry membrane. † Data taken from refs 20,21. ‡ Data taken from ref. 22.

are stronger than those in PA-doped PBI. The polymer content less than that for PA-doped PBI, suggesting that PA-doped PBI is
of PA-doped QAPOH is more than two times higher than that of more hygroscopic than PA-doped QAPOH. The lower water affinity
PA-doped PBI because of the significantly lower QA concentration of PA-doped QAPOH is probably due to the stronger interactions
compared to benzimidazole concentration. The number of water of doped PA molecules. A similar trend was observed in sulfonated
molecules per base moiety for the PA-doped polymers is much polymers, in which polar groups such as nitrile or phosphine oxide
higher than the amount for the undoped polymers, indicating that in the polymer matrix effectively reduce the water uptake10 .
the PA molecules play a strong role in water uptake. The number The PA retention for PA-doped QAPOH and PA-doped PBI was
of water molecules per PA for PA-doped QAPOH is 4.4, which is compared at 80 ◦ C/40% relative humidity (RH) and 200 ◦ C/0% RH

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NATURE ENERGY DOI: 10.1038/NENERGY.2016.120 ARTICLES
a b 93% of the original weight and the PA-doped PBI held 54% after
100 100
44 h exposure (Fig. 2a). The number of PA per QA for the PA-doped
90 90 QAPOH was found to be 12.8, retaining 90% of the original PA-
QAPOH
doping level. In contrast, the number of PA per benzimidazole for
QAPOH
80 80 the PA-doped PBI was 5.7, retaining only 47% of the original PA

Weight (%)
Weight (%)

content. Under 220 ◦ C/0% RH conditions, the PA-doped QAPOH

70 70
retained 77% of the original weight and the PA-doped PBI retained
60 PBI 67%. The PA retention difference between two polymer systems
60
through PA evaporation is much smaller than that through water
50 PBI 50 condensation. This comparative study suggests that the primary
40 40 benefit of the ion pair coordination over the acid–base coordination
is the enablement of lower operating temperature with increased
30 30 water tolerance.
0 10 20 30 40 50 0 10 20 30 40 50
The impact of the PA retention on proton conductivity is
Time (h) Time (h)
illustrated in Fig. 3a, which compares the proton conductivity
Figure 2 | PA retention PEMs. a,b, Percentage weight change of change of PA-doped PBI and PA-doped QAPOH PEMs during RH
PA-doped polymers as a function of time at 80 ◦ C/40% RH (a) and cycles from 5 to 90% at 80 ◦ C. In the first run, the conductivity
220 ◦ C/0% RH (b). Error bars in a represent the standard deviation for two of PA-doped PBI gradually decreased as the RH increased to 90%.
separate measurements. The dashed lines are guides for the eye. After the first run, the number of PA per benzimidazole in PA-
doped PBI had decreased from 11.6 to 3.7, a loss of 68%. In
(Fig. 2). The former testing conditions induce PA loss through water subsequent runs, the conductivity of PA-doped PBI was decreased
condensation and the latter conditions induce PA loss through PA by three orders of magnitude under the low-RH conditions. The
evaporation. Under 80 ◦ C/40% RH, the PA-doped QAPOH retained PA-doped QAPOH showed different behaviour. In the first run, the

a 103 b 200
RH cycle

150
1st
2nd QAPOH
3rd PBI
102 4th
100
5th
6th 80 Nafion
1st
Conductivity (mS cm−1)

Conductivity (mS cm−1)

2nd
101 3rd 60

40
100
30

20
10−1

QAPOH 15

PBI
10−2 10
0 20 40 60 80 100 0 10 20 30 40 50 60 70 80 90 100
RH (%) RH (%)

c
50 PBI PH2O = 17.3 kPa
PH2O = 2.3 kPa
40
Conductivity (mS cm−1)

30 QAPOH PH2O = 9.7 kPa

20
PH2O = 32.2 kPa
PH2O = 5.4 kPa
10
PH2O = 9.7 kPa Nafion PH2O = 9.7 kPa
0

0 20 40 60 0 20 40 60 80 100 120 140

Time (h) Time (h)

Figure 3 | Proton conductivity of PEMs. a, In-plane proton conductivity change at 80 ◦ C during RH cycles between 5% and 90% for PA-doped PEMs.
b, In-plane equilibrated conductivity of PEMs at 80 ◦ C. The dashed lines are guides for the eye. c, Through-plane proton conductivity change of three PEMs
as a function of time, measured in fuel cell mode at 150 mA cm−2 and 80 ◦ C. Cathode outlet water partial pressure, PH2 O is calculated as 2.3, 5.4, 9.7, 17.3
and 32.2 kPa for inlet RH values of 0, 7, 16, 32 and 64%, respectively.

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a 0.8 b 0.8 c 0.8

1.0 1.0 1.0

Power density (W cm−2), filled

Power density (W cm−2), filled

Power density (W cm−2), filled

QAPOH QAPOH
Celtec Celtec

Voltage (V), unfilled

Voltage (V), unfilled

Voltage (V), unfilled

0.8 Nafion 0.6 0.8 Nafion 0.6 0.8 0.6

0.6 0.6 0.6

0.4 0.4 0.4
0.4 0.4 0.4
0.2 0.2 0.2
0.2 0.2 0.2
QAPOH
0.0 0.0 Celtec
0.0 0.0 0.0 0.0
10 80 °C 4 160 °C
HFR (Ω cm2)

HFR (Ω cm2)

HFR (Ω cm2)
120 °C 1.0 PH2O = 49.6 kPa
8 PH2O = 9.7 kPa 3 PH2O = 33.5 kPa
2 2
0.5
1 1
0 0 0.0
0 0.2 0.4 0.6 0.8 0 0.5 1.0 1.5 2.0 2.5 0 1 2 3 4
Current density (A cm−2) Current density (A cm−2) Current density (A cm−2)

d
0.8 QAPOH Voltage (unfilled) 4
Celtec HFR (filled)

HFR (Ω cm2)
0.6 3
Voltage (V)

0.4 2

0.2 80−160 °C thermal cycles, PH2O = 9.7 kPa 1

0.0 0
0 20 40 60 80 300 320 340 360 380 400 420 440 460 480 500
Number of cycles

Figure 4 | Fuel cell performance and durability. a–c, i–V curve, power density and HFR for QAPOH (orange), Celtec (black) and Nafion (olive). The dashed
lines are guides for the eye. Test conditions: 80 ◦ C, 16% inlet RH (PH2 O = 9.7 kPa), 68.9 kPa backpressure, and after 10 h break-in (a); 120 ◦ C, 16% inlet RH
(PH2 O = 33.5 kPa), 206.8 kPa backpressure, and after 14 h break-in (b); 160 ◦ C, 8% inlet RH (PH2 O = 49.6 kPa), 206.8 kPa backpressure, and after 40 h
break-in (c); QAPOH thickness: 120 µm. d, HFR and cell voltage change of QAPOH (orange) and Celtec (black) MEAs during AST; QAPOH thickness:
80 µm. Data represented by the filled symbols in all the panels refer to the right-hand side axes.

conductivity improved as the RH increased, reaching conductivity ion-pair-coordinated PA-doped QAPOH PEM could enable fuel cell
more than twice that achieved by PA-doped PBI. The proton operation at 80 ◦ C at high current density.
conductivity gradually decreased during several subsequent runs,
before stabilizing after the fifth run, indicating that the loss of PA Fuel cell performance and durability
and corresponding loss of conductivity is much slower for QAPOH Membrane electrode assemblies (MEAs) using PA-doped QAPOH
than for PBI. The number of PA per QA stabilized at 8.5, a 40% loss membranes were prepared with carbon-supported Pt catalysts
of the original PA content. and QA-tethered poly(styrene) (Supplementary Figs 2–4 and
Figure 3b shows the equilibrated proton conductivity of PEMs Supplementary Table 1). The H2 /O2 fuel cell performance of MEAs
at 80 ◦ C as a function of RH. The proton conductivity of PA- at 80, 120 and 160 ◦ C is compared at relatively low P H2 O in Fig. 4. The
doped PBI gradually decreased with increasing RH due to PA PA-doped QAPOH MEA shows significantly better performance
leaching from the PEM. The proton conductivity of PA-doped than Nafion and PA-doped PBI (Celtec-P 1000) MEAs at 80 and
QAPOH increased as RH increased to ∼50%, then decreased with 120 ◦ C (Fig. 4a,b). The poor performance of the Nafion MEA is
further RH increase. This suggests that, unlike PA-doped PBI, due to the high cell high-frequency resistance (HFR), as a result
PA-doped QAPOH effectively uses both PA and water for proton of insufficient hydration of the PEM; the poor performance of the
conduction, without excessive PA loss in the intermediate RH range. Celtec MEA is due to the high cell HFR as a result of PA loss
The proton conductivity of Nafion increased as RH increased, as during the 10–14 h break-in at the partially humidified condition.
expected. However, reasonable conductivity (>60 mS cm−1 ) was At 160 ◦ C, the Celtec MEA showed excellent performance at the
only obtained when the RH level was more than 90%. beginning of the test; however, the performance gradually decreased
Figure 3c shows the conductivity changes of these PEMs during and the cell HFR increased from 70 to 300 m cm2 over 40 h
fuel cell operation. The proton conductivity of PA-doped PBI (Supplementary Fig. 5a). As a result, a comparable performance for
measured at a water partial pressure, P H2 O , of 2.3 kPa was stable; the Celtec MEA was obtained after 40 h break-in (Fig. 4c). This
however, the proton conductivity with P H2 O of 5.4 and 9.7 kPa suggests that PA loss is still occurring for PA-doped PBI even at
started out high, but decreased with time. This result suggests that 160 ◦ C when P H2 O is 49.6 kPa. In contrast, the performance of the
water-absorption-induced PA loss from PA-doped PBI occurs at QAPOH MEA did not change over time (Supplementary Fig. 5b).
very low water partial pressure. In contrast, the proton conductivity The H2 /O2 fuel cell performance of the QAPOH MEA was
of PA-doped QAPOH was reasonably stable up to P H2 O = 17.3 kPa; also measured without external humidification as a function of
the conductivity decay rate of PA-doped QAPOH at P H2 O = 9.7 kPa operating temperature (Supplementary Fig. 6). The performance
was only −1.0 µS cm−1 h−1 , more than three orders of magnitude increased when the operating temperature increased from 80 to
lower than that of PA-doped PBI at the same water partial pressure. 180 ◦ C, with 800 mW cm−2 peak power density obtained at 180 ◦ C.
This result suggests that PA-doped PBI can be used in fuel cells at The HFR of the MEA decreased from 0.68 to 0.23  cm2 as the
80 ◦ C only in a very low level of water partial pressure, equivalent operating temperature increased from 40 to 160 ◦ C. No significant
to that produced from operation at 150 mA cm−2 . In contrast, the performance improvement and HFR reduction were observed when

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NATURE ENERGY DOI: 10.1038/NENERGY.2016.120
the cell temperature was further increased to 200 ◦ C. The peak
power density of the H2 /air fuel cell of QAPOH MEAs typically
shows ∼50% of that of the H2 /O2 fuel cell (see example in
Supplementary Fig. 7).
The durability of QAPOH MEAs was first evaluated under 120 ◦ C
H2 /air conditions for 500 h (Supplementary Fig. 8). The data shows
no performance degradation due to PA loss or PEM degradation.
Therefore, we evaluated the durability of QAPOH MEAs using a
more rigorous accelerated stress test (AST). The AST consisted of
thermal cycling from 80 to 160 ◦ C with a temperature ramp of
10 ◦ C min−1 , with P H2 O of 9.7 kPa (Supplementary Fig. 9). Figure 4d
compares the durability of the Celtec and QAPOH under this AST.
The voltage of the Celtec MEA at a constant current density of
0.15 A cm−2 and 68.9 kPa backpressure decreased from 0.78 to ∼0 V
within only 70 cycles, revealing much inferior stability compared to
operation under anhydrous conditions11 . After the AST, the number
of PA per benzimidazole for the Celtec MEA was reduced to 1.7,
retaining less than 15% of the original PA-doping level. In contrast,
the performance of the QAPOH MEA was relatively stable, with
a voltage decay at 160 ◦ C of −0.39 mV/cycle (−1.51 mV h−1 ). The
number of PA per QA after 500 thermal cycles was 8.4, retaining
60% of the original PA-doping level.
Conclusions
This comparative study suggests that while acid–base-coordinated
PBI fuel cells require anhydrous conditions for optimal perfor-
mance and durability, fuel cells based on ion-pair-coordinated
QAPOH PEMs are more tolerant of water condensation or absorp-
tion, enabling operation at lower temperatures with substantially
higher water partial pressure than are possible for high-temperature
PA-doped PBI fuel cells. Furthermore, the excellent thermal and
mechanical properties of the ion-pair-coordinated PEMs (Supple-
mentary Figs 10 and 11) enable fuel cell operation at temperatures
up to 180 ◦ C. At the same time, these ion-pair-coordinated PEM fuel
cells can operate at higher temperatures and lower humidity levels
than low-temperature Nafion-based PEM fuel cells. This opera-
tional flexibility, which is unattainable with existing fuel cell technol-
ogy, could enable fuel cell system simplification and cost reduction,
leading to a paradigm shift in the effort to spur commercialization
of low-cost fuel cells for clean energy automotive and stationary
power applications.
Methods
Materials. The PA-doped PBI membranes (Celtec-P) produced through the
polyphosphoric acid process7 were supplied by BASF Fuel Cells (Somerset, New
Jersey). The membrane thickness was 260 µm. Nafion membranes (Nafion
NR-212, 50 µm thickness) were purchased from Ion Power (New Castle,
Delaware). Gas diffusion electrodes (GDEs, ELE0142) for Nafion MEAs were
supplied by Johnson Matthey. The GDEs contain HiSPEC 9100 60% Pt/C (Pt
loading: 2.0 mgPt cm−2 ). PA-doped PBI MEAs were supplied by BASF Fuel Cells
(Somerset, New Jersey). The MEAs were Celtec-P 1000 MEAs produced at BASF
Fuel Cell GmbH (Frankfurt). Anode catalyst: Pt/C (Pt loading: 1.0 mgPt cm−2 );
cathode catalyst: Pt-alloy/C (Pt loading: 0.75 mgPt cm−2 )12 . PA-doped PBI PEM
thickness: ∼50 µm. For the fabrication of QAPOH MEAs, commercial 60% Pt/C
(HiSPEC 9100) and 40% Pt-Ru/C (Pt:Ru = 2:1, HiSPEC 10000) were purchased
from Alfa Aesar and Johnson Matthey, respectively. The Pt loading on the anode
and cathode were both 0.6 mgPt cm−2 . Single-side ELAT gas diffusion layers
(GDLs) were purchased from ETEK.
Preparation of PA-doped QA-tethered polymers. The QAPOH membranes were
synthesized by an irreversible Diels–Alder reaction between
tetramethylbis(cyclopentadienone) and 1,4-diethynylbenzene13 . This polymer was
then brominated, converting a fraction of the methyl positions into bromomethyl
groups. The resultant functionalized polymer was then cast into films from
chloroform. The films were then soaked in a 5 M solution of aqueous trimethyl
amine to generate the QAPOH membranes. The QAPOH membranes were then
immersed in an 85 wt% aqueous solution of PA at room temperature for 2 h. All
PA-doped QAPOH were used after removing the excess PA on the membrane
surface by blot drying. The QA-tethered poly(styrene) hydroxide (QASOH)
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ionomeric binder was synthesized via nucleophilic substitution of triethylamine
(TEA) and 4-fluorophenethylamine onto poly(vinylbenzyl chloride) (PS-bzCl).
A solution of poly(vinylbenzyl chloride) (10 g, Sigma-Aldrich) in
N,N -dimethylformamide (DMF) (360 ml) was reacted with TEA (3.3151 g,
Sigma-Aldrich) at 130 ◦ C for 3 h. To the reaction mixture,
4-fluorophenethylamine (4.5594 g, Sigma-Aldrich) was added and reacted for an
additional 12 h. This 5 wt% polystyrene copolymer solution in DMF was used as
an ionomer solution. PA-doped QASOH was obtained after electrode fabrication
process via an imbibing process (see the MEA fabrication section below).
Spectroscopy. The proton nuclear magnetic resonance (1 H NMR) spectra were
recorded using a Bruker Avance 500 spectrometer (500 MHz) in deuterated
dimethylsulfoxide (DMSO-d 6 ). Chemical shifts of 1 H NMR spectra were
referenced to tetramethylsilane (TMS) at 0 ppm as an internal reference. The
Fourier transform infrared spectroscopy (FTIR) spectra were recorded using a
Thermoscientific FTIR 8700 at a resolution of 4 cm−1 in the range of
4,000–600 cm−1 .
Titration. The PA-doping level of PEMs was determined by acid–base titration
through the following procedure: PEM samples measuring 0.5 inch × 2 inch were
weighed; the PEM samples were titrated with 0.1 M NaOH solution using
phenolphthalein as an indicator; the samples were washed with water and dried
in a vacuum plate at 100 ◦ C for 3 h and weighed again. The number of PA per
repeat unit (X ) was calculated from the following equation:
VN aOH × CN aOH
X=   (1)
W
Eqivmol × Mdry
W
where V NaOH (l) is the volume of NaOH, C NaOH (mol l−1 ) is the molar
concentration of NaOH, Equivmol is the equivalent mole of titrant for PA (which
is 3 in this case; three moles of NaOH reacts with one more of phosphoric acid to
produce trisodium phosphate), W dry (g) is the dry polymer weight, and M W
(g mol−1 ) is the molecular weight of the polymer repeat unit.
The number of PA per QA (or benzimidazole), (nPAQA ) was calculated from
the following equation:
(X × 1000)
nPAQA = (2)
(IEC × MW )
where IEC (mmol g−1 ) is the ion exchange capacity of undoped PEM.
The hydration number (λ), defined as the number of water molecules per
QA (or benzimidazole) of PA-doped PEMs, was calculated from the
following equation:
(Wwet − Wdry − 98 × Wdry × nPAQA × 1000
IEC
)
λ= (3)
(18 × Wdry × 1000
IEC
)
where W wet (g) is the wet weight of PA-doped PEM.
Thermogravimetric analysis. PA loss for PA-doped PBI and PA-doped QAPOH
was measured under two conditions: 80 ◦ C/40% RH and 220◦ C/0% RH. For the
80 ◦ C conditions, 0.5 inch × 2 inch rectangular test PEM strips were put in a
convection oven at 80 ◦ C for 1 h to remove most of the water. After measuring the
weight of the test strips, the samples were equilibrated at 80 ◦ C/40% RH for 1 h in
an environmental oven and taken out to dry at 80 ◦ C and 0% RH for 1 h to
remove water. The weight of the dried samples was measured. The equilibrating
and drying steps were repeated until the total equilibrated time reached 44 h.
After finishing the last measurement, the samples were immersed in boiling water
for 2 h to remove all PA, dried at 80 ◦ C for 6 h and weighed to calculate the PA
loss. Two samples were tested for each PEM. For the 220 ◦ C conditions, the
weight of PEMs was measured by thermogravimetric analysis (TGA, TA
Instrument 2100 series). The temperature scan was performed with three steps:
PEMs were heated from 30 to 100 ◦ C at a heating rate of 10 ◦ C min−1 in air,
followed by maintaining at 100 ◦ C for 1 h to remove moisture; PEMs were heated
from 100 to 200 ◦ C at a heating rate of 10 ◦ C min−1 in air, followed by
maintaining at 200 ◦ C for 50 h to observe the loss of PA. Thermal oxidative
stability of undoped and PA-doped QA functionalized polymers were measured
by TGA. The polymer membranes were preheated at 150 ◦ C for 1 h in the TGA
furnace to remove moisture. The temperature scan was performed from 80 to
800 ◦ C at a heating rate of 10 ◦ C min−1 in air. The isothermal experiment was
performed at 240 ◦ C in air.
Proton conductivity. In-plane proton conductivity of the PEMs was measured
from a.c. impedance spectroscopy using a Solartron 1260 gain phase analyser
over a frequency range from 1 Hz to 1 MHz. Sample strips had dimensions of
approximately 0.5 × 1 inch and were seated between two Pt coated electrodes of
5
ARTICLES
a window cell. The conductivity (σ , mS cm−1 ) of the PEMs in the longitudinal
direction was calculated from the equation:
L Modelling. DFT calculations were performed using the Gaussian 09 suite of
σ=
R×d ×W
where L (cm) is the distance between the electrodes R (m) is the resistance that
was read from the low intersect of the high-frequency semicircle on a complex
impedance plane with the Re(Z) axis, d (cm) is the wet thickness of the
membrane, and W (cm) is the width of the membrane.
The proton conductivity change during RH cycles was measured at 5% RH
(first run) and 10 to 90% RH (subsequent runs) with 10% RH increments. Two
hour equilibration time was applied at a given RH. Before each RH cycle, samples
were equilibrated for 14 h at 5% RH. Each RH cycle took 32 h. The equilibrated
proton conductivity was obtained from the conductivity of PEMs after exposure
to a given RH. The conductivity of PEMs was measured every two hours and the
equilibrated conductivity at the given RH was taken when the conductivity
change was less than 2% from the previous measurement.
The proton conductivity of the PEMs was obtained in fuel cell mode by the
HFR method14 . For the measurement, MEAs comprising of PEMs, catalyst layers
and gas diffusion layers were fabricated and run at 150 mA cm−2 . A small a.c.
signal is applied to the MEAs to modulate the d.c. load current under H2 /O2 fuel
cell operating conditions. The single high frequency is determined by imposing
the a.c. perturbation over a broad range of frequencies by an electrochemical
impedance. The measured HFR was converted to proton conductivity without
subtracting the electronic resistance contributions. Through-plane conductivity
(σ , mS cm−1 ) of the PEMs was calculated from the equation:
t 104 (Logos Verlag Berlin GmbH, 2011).
σ=
R
where t (cm) is the thickness of membrane, and R (m cm−2 ) is the HFR that
was read from the single frequency measurement.
The water partial pressure, P H2 O , was calculated from the inlet RH and water
mass flux (J 0 , g cm−2 -s) produced via oxygen reduction reaction to the mass flux
of water of a given inlet RH. The mass flux of water was calculated from
the equation:
j0 MWater
J0 = (6)
2F
where j0 (A cm−2 ) is the Faradaic current density, M Water (g mol−1 ) is the molar
mass of water, and F (C mol−1 ) is the Faraday constant.
Mechanical properties. The mechanical properties of PEMs were characterized
by dynamic mechanical thermal analysis (DMTA, TA Instrument Q800-RH). The
temperature and humidity were controlled in an environmental chamber. The
tensile test was performed using 0.5 inch × 1 inch rectangular test strips at a load
ramp of 0.5 MPa min−1 at 80 ◦ C and 0, 5, 20 and 50% RH. The stress–strain
behaviour of the membranes was measured after 1 h of equilibrium time at the
target RH. Three samples were tested for each condition.
MEA fabrication. MEAs were prepared from catalyst inks containing Pt/C
catalysts (HiSPEC 9100), 5 wt% QASOH dispersion in DMF, methanol and
ethylene glycol. The catalyst ink composition was 1.5 wt% Pt/C, 3.5 wt% QASOH
dispersion, 22 wt% ethylene glycol and 73 wt% methanol. Gas diffusion electrodes
(GDEs) were prepared by painting catalyst inks onto GDLs on a vacuum plate at
100 ◦ C. The catalyst-coated GDEs were sandwiched with a PA-doped QAPOH
PEM after immersion of both GDEs in 85 wt% PA solution at room temperature
for 5 min, followed by removing the excess PA on the GDE surface with blot
drying. In this way, the PA doping was controlled to a low level, about 2.7 PA per
QA, to prevent PA flooding during fuel cell tests. The active area of each MEA
was 4.8 cm2 .
Fuel cell performance and durability. H2 /O2 fuel cell performance of the MEAs
was measured using a fuel cell test station (Fuel Cell Technologies). Polarization
curves and HFR of MEAs were obtained at temperatures ranging from 40 to
200 ◦ C. H2 and O2 were supplied at a rate of 200 and 300 sccm, respectively.
H2 /air long-term stability tests were performed as well. The cell current density
and HFR were measured every minute under a constant voltage of 0.4 V without
backpressure and without external humidification (cathode outlet P H2 O = 3.6 kPa)
for the first 276 h, then with 3.7% intermittent inlet RH (cathode outlet
P H2 O = 76.4 kPa) for 20 min. The stability of PEMs was evaluated by AST. For this
experiment, a temperature cycling AST consisting of triangular thermal cycles
from 80 to 160 ◦ C with a ramp of 10 ◦ C min−1 was performed. The anode and
cathode inlet dew point was fixed to 40 ◦ C. Cell voltage under a constant current
density of 0.15 A cm−2 at 68.9 kPa backpressure was measured every minute. The
cell HFR was measured each time the cell temperature reached 80 or 160 ◦ C. The
6 NATURE ENERGY | VOL 1 | SEPTEMBER 2016 | www.nature.com/natureenergy
© ƐƎƏƖɥMacmillan Publishers LimitedƦɥ/13ɥ.$ɥ/1(-%#1ɥ341#. All rights reservedƥ
NATURE ENERGY DOI: 10.1038/NENERGY.2016.120
inlet RH and P H2 O were reported for fuel cell performance and
durability measurement.
(4)
programs15 . Geometrical parameters were optimized by employing the ωB97XD
functional16 with the 6-311++G(2d, 2p) basis set17 , where the functional includes
the effects of long-range correction and dispersion correction. The basis set
superposition error (BSSE)18 for interaction energy calculations was corrected
using the counterpoise method19 .
Received 4 April 2016; accepted 14 July 2016;
published 22 August 2016
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Acknowledgements
This work was supported by the US Department of Energy, Energy Efficiency and
Renewable Energy, Fuel Cell Technology Office. We thank E. S. De Castro for useful
NATURE ENERGY DOI: 10.1038/NENERGY.2016.120
discussion and for supplying PBI samples. We also thank C. Kreller for helping with the
polymer thermal analysis. Y.-K.C. acknowledges financial support from the Ministry of
Economy, Trade and Industry of Japan through the Japan-US Cooperation on Clean
Energy Technology Program. Los Alamos National Laboratory is operated by Los Alamos
National Security, LLC under Contract DE-AC52-06NA25396. Sandia National
Laboratories is a multi-program laboratory operated by Sandia Corporation, a wholly
owned subsidiary of Lockheed Martin Company, for the US Department of Energy’s
National Nuclear Security Administration under contract DE-AC04-94AL85000.
ARTICLES
cells. Y.-K.C. performed the modelling work. C.F. and K.-S.L. prepared the polymeric
materials. K.-S.L., J.S.S. and Y.S.K. analysed all experimental data and wrote the paper.
Additional information
Supplementary information is available for this paper. Reprints and permissions
information is available at www.nature.com/reprints. Correspondence and requests for
materials should be addressed to Y.S.K.

Author contributions
Y.S.K. developed the intellectual concept, designed all the experiments, and supervised Competing interests
this research. K.-S.L. performed the MEA fabrication and testing experiments of fuel The authors declare no competing financial interests.

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