Review - PA Retention in HTPEM

Concept
Chemistry—A European Journal doi.org/10.1002/chem.202202064
www.chemeurj.org
Phosphoric-Acid Retention in High-Temperature Proton-

Exchange Membranes
Hongying Tang,*[a] Jian Gao,[a] Yidong Wang,[a] Nanwen Li,*[b] and Kang Geng*[b]
Chem. Eur. J. 2022, 28, e202202064 (1 of 13) © 2022 Wiley-VCH GmbH

15213765, 2022, 70, Downloaded from https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202202064 by National Taiwan University, Wiley Online Library on [09/07/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Concept
Abstract: Great efforts have been conducted to develop high retention for example via introduction of phosphonic acid by
temperature proton exchange membrane fuel cell (HT- covalent bond, using ion-pairs interaction and siphoning
PEMFC) due to its features of enhanced electrocatalyst effect, and blending with inorganic nanoparticles are de-
reactivity, simplified hydrothermal management system and scribed in detail. Among these strategies, the siphoning effect
high CO tolerance of catalysts, and remarkable progress has from the intrinsic microporous PEMs is the most efficient and
been achieved. However, the easy leaching of phosphoric enables the cell to operate flexibly within a broad temper-
acid (PA) from the membranes during operation limits its ature range. Therefore, this concept may provide new ideas
commercial scale-up in complicated environments. This for the scientists to retain PA, to improve the cell performance
concept here mainly focuses on the recent developments for and expand the potential applications of PA doped PEMs at
mitigation of PA loss in PEMs. The probable mechanisms of elevated humidity and wide temperature range.
PA loss are proposed. The approaches to improve PA
Introduction with a PEM, which include the electrodes, electrolyte, catalyst,

and gas diffusion layers. Hydrogen is fed to the anode side of
In recent years, the interest in hydrogen production and the MEA and catalytically split into protons and electrons. This
utilization in many energy sectors is increasing with the oxidation half-cell reaction is named hydrogen oxidation
demand of renewable electricity. Hydrogen energy as the most reaction (HOR) and represented by Equation (1):
promising clean energy in the 21st century has been developed At the anode:
rapidly in the whole world. Hydrogen fuel cell is an electro-
chemical energy device that converts the chemical energy of a dEo
H2 ! 2Hþ þ 2e Eo ¼ 0V ¼ 0mVK 1
(1)
fuel (often hydrogen) and an oxidizing agent (often oxygen) dT
into electricity, water and heat through a pair of redox
reactions.[1] Fuel cell can produce electricity continuously as Meanwhile, oxygen is supplied to the cathode and reacts
long as hydrogen and oxygen are available and is regarded as a with the protons permeating through the PEM from the anode.
green energy technology. Fuel cell can solve the human energy This reduction half-cell reaction which named oxygen reduction
crisis by utilizing hydrogen energy efficiently, and has broad reaction (ORR) is represented by Equation (2):
market demand and application prospect.[2] Many investments At the cathode:
have been made by the governments and major automotive
companies in hydrogen energy and fuel cell vehicles. The 1 dEo
O þ 2Hþ þ 2e ! H2 O Eo ¼ 1:2291V
commercialization of fuel cell is proceeding apace, while its 2 2 dT (2)
1
large-scale application is still constrained by the factors such as ¼ 0:8456mVK
cost and longevity. There are many types of fuel cells, such as
proton-exchange membrane fuel cell (PEMFC), Phosphoric acid Overall reaction is shown in Equation (3):
fuel cell (PAFC), Solid acid fuel cells (SAFC) and Solid oxide fuel
cell (SOFC). PEMFC, also known as polymer electrolyte mem- 1 dEo
H2 þ O ! H2 O Eo ¼ 1:2291V ¼ 0:8456mVK 1
(3)
brane (PEM) fuel cell, is a typical type of energy conversion 2 2 dT
system being developed mainly for transport applications, as
well as for stationary fuel-cell applications and portable fuel-cell The reaction as expressed in the equation is carried out via
applications owing to its large power-output, fast startup/shut- the reincorporation of the H + and e together with O2 thus
down cycles and continuous power supply. water being produced. The given potentials in each equation
The typical membrane electrode assembly (MEA) of PEMFCs are relative to the standard hydrogen electrode.
are composed two gas diffusion electrodes (GDEs) sandwiched According to the operation temperature, PEMFC is divided
into two classical types of PEMFC, which includes low temper-
ature (LT) PEMFC generally using perfluorosulfonic acid (PFSA)
[a] Dr. H. Tang, J. Gao, Prof. Y. Wang as PEMs (e. g., Nafion®) and high temperature (HT) PEMFC using
Tianjin Key Laboratory of Water Resources and Environment acid-doped polyelectrolytes (e. g., phosphoric acid-doped poly-
Tianjin Normal University
benzimidazole (PA/PBI), while both systems have their own
300387 Tianjin (China)
E-mail: [email protected] advantages and limitations. Nafion®-based PEMFCs have been
[b] Prof. N. Li, Dr. K. Geng commercialized within vehicles, due to their excellent proton
State Key Laboratory of Coal Conversion conductivity with fully humidification at relatively low temper-
Institute of Coal Chemistry atures (< 80 °C). However, the sulfonated proton exchange
Chinese Academy of Sciences
membranes(PEMs) are not as conductive under lower RH
030001 Taiyuan, China
E-mail: [email protected] conditions and would dehydrate at higher temperatures, thus
[email protected] extra efforts for water and heat management, such as large

Concept
radiators to dissipate waste heat, are required.[3] In contrast, proton motion and a significant proton dielectric response to
acid-base type PEMFC which is typically prepared via using a the medium leading to form an extended, polarized hydrogen-
nonvolatile inorganic acid doped a basic membrane[4] operating bonded chains. This remarkable rapid proton conduction which
at temperatures above 100 °C has simplified humidity system, results from the interaction between these chains and a
minimized waste heat rejection, enhanced electrocatalyst frustrated hydrogen-bond network is similar as Grotthuss
reactivity, and high tolerance to CO (> 1 % CO at 150 °C),[5] mechanism.[9] Polybenzimidazoles (PBI), a series of polymers
which make it highly attractive for distributed power with benzimidazole groups in the polymer backbone,[4a] have
generation.[6] been investigated in detail and considered as the most classic
Hitherto, phosphoric acid (H3PO4, PA) is the most widely HT-PEMs due to the acid-base interaction with phosphoric acid.
used dopant for HT-PEMFCs owing to its high thermal stability, Although HT-PEMFCs based on PA/PBI membranes can operate
low volatility and high intrinsic proton conductivity.[7] Neat at 160 °C without any additional humidification for over
liquid phosphoric acid exhibits the highest intrinsic proton 17,000 h, the doped PA leaks out of the membranes easily
conductivity of about 0.15 S cm 1 above 42 °C (the melt point) when humidity is present, which renders the fuel cells cannot
within any known substance.[8] The strong and polarizable function well below 140 °C.[10]
hydrogen bonds P O H···O=P in PA can produce coupled In addition to the narrow operation temperature/RH
windows for the two PEMFCs, sub-zero start-up capability is
another obstruction to the commercialization of both
systems.[11] In general, using engineering means and external
Hongying Tang is currently an assistant
professor in Tianjin Normal University.
assistance to manage the water in the cell during shut-down
She received her Ph.D. in Physical and start-up can enhance the cold-start-up performance
Chemistry from the Institute of Elemen- indirectly. There is little effort has been made to improve the
to-Organic Chemistry, Nankai University cold-start-up capability of the cells by directly improving the
in 2008. Her current research revolves performance of the MEA.[12] As our knowledge, the freezing
around polymer-based polymer electro-
point of the PA solution exhibits a gradual decrease tendency
lytes and electrode binders in the
context of electrochemical energy con- when the concentration of PA gradually increases. With the
version. decreased water content in the solution, the freezing point of
the phosphoric acid solution can reach 90 °C.[13] These
properties make it feasible to solve the cold start challenge and
realize the ultra-low temperature operation of PA doped PEMFC
Nanwen Li is a professor at Institute of
Coal Chemistry, Chinese Academy of by directly enhancing the proton conductivity of PA doped PEM
Sciences. He received his B.S. degree in below 0 °C via improving the PA retention and decreasing the
2004 in Northeast Normal University contain of the water in the PEM.[12]
and his Ph.D. degree in 2009 in Chang- Great efforts have been made to study and develop the PA
chun Institute of Applied Chemistry, doped HT-PEMFC attributing to its desirable characteristics in
Chinese Academy of Sciences. In 2009–
these two decades. Despite extensive reviews conducted with
2010, he worked as a postdoctoral
researcher in Prof. Young Moo Lee’ the emphasis on essential issues,[14] membrane materials,[4a,15]
group in Hanyang University. From and the cell durability,[16] the issue about the phosphoric acid is
2011 to 2014, he served as Humboldt left in the basket.[17] Based on the key problem of phosphoric
scholar, research assistant, postdoctoral acid loss in PA doped PEMs in the present of humidity, much
in Martin Luther University of Germany, investigation has been conducted to improve the performance
National Research Center of Canada,
Pennsylvania State University and Geor- and enlarge the operational temperature range. Therefore,
gia Institute of technology. His research supplementing these previous reviews, this work will focus on
interest includes ion exchange mem- recent developments in preventing PA leakage in PA doped
branes and gas separation membranes. PEMFC and underlying mechanisms, new insights in improving
Kang Geng is a postdoctoral fellow at cold-start-up performance and further discussions in potential
Institute of Coal Chemistry, Chinese application in fuel cell fields.
Academy of Sciences. He received his
B.Sc. in Science and Engineering of
Polymer Materials from Dalian Maritime
The proposed mechanism of phosphoric acid loss
University in 2016 and his Ph.D. in
Organic Chemistry from Institute of
Coal Chemistry in 2021. He then con- PA is a medium–strong acid, and that hydrogen ions can be
tinued his postdoctoral research at released in water according to the reaction (Eq (4)):
Institute of Coal Chemistry. His current
research interests focus on the develop- H3 PO4 þ H2 O Ð H3 Oþ þ H2 PO4 pKa ðH3 PO4 Þ ¼ 2:12 (4)
ment and application of ion exchange
membranes for fuel cell, water electro-
lyzer and flow battery. When the molar ratio of H3PO4/H2O in PA solution is greater
than 1, so the concentrations are higher than 85 %, PA can self-

Concept
dissociate to provide the protonated product of phosphacidium PA evaporation

ions H4PO4 +. The H4PO4 + is a strong acid as sulfuric acid with a
pKa value of 3, see Equations (5) and (6): The vapor on PA solutions consists mainly of water and PA. As
shown in Figure 2, the vapor phase at 160 °C contains about
2H3 PO4 Ð H2 PO4 þ H4 PO4 þ (5) 0.7 ppm (mol) PA, while at 190 °C, the PA content 3.7 ppm (mol)
is much higher.[4a,20] Though the acid vapor pressure is very low,
H4 PO4 þ þ H2 O Ð H3 Oþ þ H3 PO4 pKa ðH4 PO4 þ Þ � 3 (6) the acid loss cannot be ignored during durability tests of the
cell with significant airflow. Furthermore, the acid loss rate
Combined with the strong hydrogen-bond network in during the cell operations increases with the temperature.
concentrated phosphoric acid, the high concentration of When current density loading of the cell is 0.2 A cm 2 and the
intrinsic protonic charge carriers[18] produced by high degree of stoichiometries is λAir = 2 and H2 = 1.2, the acid loss along with
self-dissociation is mainly contributed to the proton conduction the gas flowing out of cells can be easily estimated according
via the Grotthuss mechanism.[7c,19] During the cell operations, to the saturated acid vapor pressure (Figure. 2). For example,
water will generate from both the electrode reaction and the acid loss rate increases from 6 to 30 μg m 2 s 1 approx-
condensation. Thus, the behavior of acid hydration and imately as the temperature increases from 160 to 190 °C. By
dehydration relating with the acid–water compositions is collecting the trace acid evaporated with the cathode outlet
particularly important, which will make the proton conductivity gases, S. Yu et. al. found that the PA loss rate reached
change greatly, thus the cell performance. In the past few 80 ng cm 2 at 190 °C, which was 10 times higher than that at
decades, during the research of PA doped HT-PEMFCs, as shown 160 °C.[10c] Notably, the off-gas cannot carry all acids in the gas
in Figure 1, three main mechanisms of PA loss have been phase out of cells by evaporation. Moreover, the acid loss rate
proposed which give new ideas for improvement of the PA varies depending on the types of membranes, MEA fabrication
retention. process, and electrode properties.
PA leaching out along with water
Mori et al. found that phosphoric acid in the PA-doped PEM

would migrate to the cathode and anode during the process of
membrane electrodes assembly. Moreover, during the cell test
process, the phosphoric acid adsorbed by the anode would
migrate to the cathode through the membrane, and then be
carried out of the cell by the gas of the cathode. According to
this study, to enhance the retention of PA, the materials used
for the cathode should have low PA adsorption, while the
materials applied for the anode should own high PA
adsorption.[25] It is known to all that the interaction between PA
Figure 1. The proposed mechanisms of PA loss in HT-PEMFCs.
and water is closed to that between PA and polymers, leading
to an easy leakage of PA along with water, especially at low
temperature (< 80 °C), and high humidity generated during the
cell start-up and shut-down. Moreover, Li et.al raised that there
was a large amount of “loosely bound” PA molecules in the PA/
PBI membranes via exploring the characteristics of the
absorbed water and acid of the electrolyte membrane, which
help to improve the proton conductivity. Thus, as mentioned
above, the “loosely bound” PA inside the membrane is easily to
leach out with water due to the very weak interaction between
the “loosely bound” PA and polymer, which is regarded as the
PA leaching mechanism with the water as shown in Figure 3a.[26]
When a PA/PBI membrane is exposed to a humid environ-
ment (I), the water molecules penetrate into the PA/PBI system
and take “loosely bound” PA molecules away from the system
(PA leaching). Subsequently, when the PA doped membrane is
Figure 2. Estimations and measurements of acid loss carried by gas flow and heated to above 100 °C (II), the water molecules in the PA phase
the extrapolation of acid vapor pressure to low temperature.[4a] Red circles starts to move out of the membrane, the “strongly bound” PA
are from Brown et al.[21] Black diamonds for PAFC are from Oono et al.[22]
whereas squares are from Büchi et al.[23] and triangles are from Søndergaard molecules are left.
et al.[24] for PBI-based HT-PEMFCs. Reproduced from Ref. [4a] Copyright
(2022), with permission from Springer.

Concept
Figure 3. Schematic illustration of (a) previous PA loss mechanism and (b) proposed PA loss mechanism during subsequent exposure to water and high
temperature (> 100 °C). Reproduced from Ref. [28] Copyright (2022), with permission from Royal Society of Chemistry.
Complex equilibrium mechanism of PA and water The approaches to reduce PA loss
Besides the PA evaporation and PA leaching mechanisms Based on the proposed mechanisms above, several approaches
mentioned above, based on the study of the energetics of PA– as shown in Figure 4 have been developed to reduce PA
benzimidazole acid–base and biphosphate–ammonium ion leaching in PA/PBI membranes, such as increasing PA doping
pairs, Lee et al. proposed a new mechanism that the PA levels, forming porous microstructures via phase inversion or
leaching in the base polymers occurred because of the inability porogen addition removal,[29] controlling membrane morphol-
of the polymer to hold PA and water beyond the equilibrium ogy, crosslinking,[4a,10a] and establishing organic-inorganic hybrid
level within a certain physical cluster volume. This mechanism systems[30] in the lately three decades. These studies were
was brought up via energetic research on proton-accepting and performed in physical modification, chemical modification and
hydroxide-donating organic bases using density functional the designation[31] of membrane structures focusing on this key
theory (DFT) calculations in the presence of water. As shown in problem, the specific methods are described as follows.
figure 3b, when a PA/PBI membrane is exposed to a humid
environment (I), the ambient water molecules continuously
enter into the PA cluster until the PA cluster cannot hold any Modification with phosphonic acid group via covalent-bonds
more water owing to the physical constraint of the rigid
polymer chains. With the addition of water, the interaction It is believed that the PA loss can be fundamentally solved by
energy of the PA cluster is increased greatly. Thus, a new grafting phosphonic acid directly on the main chain of the
equilibrium partition composition (PA loss) is reached due to polymer. Thus, a lot of research has been done on the
the exchange of some PA molecules with water molecules as modification of polymers with phosphonic acid via covalent
the addition of water. Subsequently, when the membrane is bonds.[32] As shown in Scheme 1, a series of phosphonated
heated to above 100 °C (II), the water vapor pressure is higher polymers such as phosphonated polystyrene,[33] phosphonated
than the hydrogen bonding of water in the PA cluster, thus the polyether-ether-ketone,[34] phosphonated poly(arylene
escape of water molecules in the PA phase from the membrane ether)s,[35] et al. have been synthesized successfully.[32c,36] How-
appears. This mechanism is not only consistent with the ever, the film formation abilities of these obtained phospho-
energetic studies of PA in PA/PBI, but also the only one which nated polymers were very poor due to the lower molecular
can explain the least PA loss between 160–180 °C.[27,28] The weight resulting from the severe synthesis procedures.
schematic diagram of this mechanism is shown in Figure 3b. Jannasch et.al from Lund university in Sweden modified
polysulfone (PSf) by grafting mono and bisphosphonic acid
groups on benzene ring as shown in Scheme 1. Though the Psf

Concept
Figure 4. The main approaches to reduce PA loss in PA doped PEMFCs.
anhydrous proton conductivity of phosphonated polymers at

100–200 °C.[39]
Recently, as shown in Scheme 3, a series of phosphonated
poly (phenylene sulfone) (P-PPSU) were synthesized by Tang
et.al via photocatalytic phosphonylation approach by post-
phosphonylation of brominated poly (phenylene sulfone) (Br-
PPSU) and subsequent acidification. Although the phospho-
nated membranes with IEC value of 2.75 showed a low proton
conductivity of only 0.30 mS/cm at 160 °C without extra
humidification, long life-time of more than 200 h for the H2/O2
fuel cell was obtained when it was applied as a binder in the
Scheme 1. The structures of phosphonic acid polymers. catalyst layer for HT-PEMFC. The proton conductive phospho-
nated PPSU binder improved the stability of the cell due to the
stable capability of proton conductivity in the catalyst layer by
membrane with high ion exchange capacity (IEC) having introduction of phosphonic acid in the polymer chain via
bisphosphonic acid groups exhibited higher proton conductiv- covalent bonds.[40] In conclusion, although these covalent-
ity than that of PSf with monophosphonic acid, the proton bonding phosphonated PEMs can fundamentally solve the
conductivity of bisphosphonic acid modified PSf membrane problem of PA loss, the proton conductivity is relatively low
was still less than 2.5 mS/cm @ 120 °C and difficult to meet the owing to the less proton carriers in the membrane which can
requirements of HT-PEMFCs for practical applications.[37] Tamura move freely. Thus, these phosphonated polymers are unable to
et al. introduced phosphonic acid groups with long-side chain use as PEMs for the practical applications of HT-PEMFC. On the
into polystyrene and used as PEM (Scheme 2This membrane other hand, for HT-PEM, the requirement of proton conductivity
showed relatively higher proton conductivity at 30–80 % in the catalyst layer is relatively low. Thus, these phosphonated
relative humidity (RH) due to the large number of hydrogen polymers as binders in the catalyst layer exhibit excellent
bond networks provided by the formed hydrophilic region via performance and show a promising prospect due to their
self-assembly. However, the phosphonated PEM which can higher thermal/chemical stabilities.[39e,41]
produce phase separation didn’t show satisfactory proton
conductivity under the conditions of at high temperature and
low humidity.[38] It is believed that the easy formation of Stronger interaction
phosphonic acid anhydrides resulted from the lower degree of
hydrogen-bond-network frustration leads to the much lower It is believed that the weaker interaction between PA and the
polymer matrix is the key to PA leaching with water absorption/

Concept
Scheme 2. (a) Synthetic pathways to PSUs carrying alkyl side chains terminated by monophosphonic acid (left) and bis(phosphonic acid) (right) via reactions
of lithiated polysulfones with triethyl 3-phosphonopropionate and tetraisopropyl vinylidenediphosphonate, respectively, followed by hydrolysis. The scheme
shows monosubstituted diarylsulfone segments. (b) Synthesis of polystyrene with phosphonic acid via long alkyl side chains.
desorption in HT-PEMs. Stronger interaction between the func- traditional HT-PEMs, especially for mPBI, which is currently
tional groups of PEMs and PA than that between water and PA commercially available. In this context, from the perspective of
can improve the PA adsorption and retention of the PA doped polymer chemistry, a detail overview of the structural scope of
PEMs greatly, thus widening the application temperature range PBI has been provided in excellent reviews conducted by for
of the PEMs. example, Li,[4a] Asensio[44] and Mustarelli et al.[45] To improve the
acid doping level, a series of PBI polymers with hydroxy groups
were successfully prepared by Benicewicz et al.[46] in
Acid-base interaction poly(phosphoric acid) (Scheme 4b). As expected, the cross-
linked functionalized PBI (2OH-PBI) through phosphoric acid
PBI is a kind of Lewis base polymer with a pKa value of about ester bridges showed higher acid doping level (ADL) than that
13.[42] The benzimidazole group in PBI backbone containing of the unfunctionalized analogue, para-PBI membranes, thus
lone pair electrons can interact with PA via the formation of leading to the improvement of the proton conductivity.
Lewis acid-base bonds.[4a,15a] Since the initial report of poly(2,2’- However, as discussed above, the PA doped into the mem-
(m-phenylene)-5,5’-bibenzimidazole) (mPBI) by Wainright branes is easily to leach out when humidity is present and the
et al.,[43] tremendous research and development of new PBI proton conductivity at low temperature (< 80 °C). Thus, it is
chemistries have been triggered during the last thirty years. As easy to conclude that, the acid-base interaction in the PA
shown in Scheme 4a, the PBIs comprise a large family of high- doped PBI membranes is not strong enough for PA retention,
performance polymers and great success has been made in the or there are not adequate alkaline sites to hold PA especially
application as PA doped PEMs for HT-PEMFCs. The PA doped “loosely bound” PA effectively.
PBI membranes have been widely studied and become the

Concept
Scheme 3. Synthesis of phosphonic acid PPSU (P-PPSU), x is value of PD.
Scheme 4. (a) The synthesis and main structures of most widely used PBIs; (b) The synthesis of 2OH-PBIs and the structure of the cross-linked membranes via
phosphoric acid ester bridges.

Concept
Scheme 5. The main structures of pyridine-containing aromatic polyether.
Except (benz)imidazole-containing polymers, alternative Quaternary ammonium biphosphate ion pairs interaction
polymers with various incorporated N-heterocycles have trig-
gered substantial research which can also interact with PA via As discussed above, the interaction between PA and water is
acid-base interaction. The protonated pyridine derivatives own very closed to that between the weak base group benzimida-
higher pKa value than that of PA as well as pronated imidazole zole and PA in PA doped PBI membrane. The energy of the
derivatives. When pyridine-containing membranes are doped molecular interaction between benzimidazole and PA is calcu-
with PA, the fully protonated forms are predominating. There- lated to be 17.4 kcal mol 1 by Lee et al., which is only
fore, as shown in Scheme 5, intensive research and develop- 4.8 kcal mol 1 larger than that between PA and H2O
ment of pyridine-containing aromatic polyether as PA doped (12.6 kcal mol 1).[56] As a result, PA is easily to leach out along
HT-PEMs have been conducted through direct copolymerization with water condensation from frequent cold start-ups and
via pyridine-containing monomers,[47] side-group electrochemical reactions at the fuel cell electrodes, thus
[48] [49]
modifications and crosslinking in the last two decades. leading to a sharp drop of the proton conductivity and cell
Based on the matured pyridine-containing membranes, Advent performance. To address this issue, this research group
Technologies has developed a core technology of high-temper- proposed to improve the PA retention by introducing stronger
ature fuel cell systems.[50] basicity into the polymer matrix to form quaternary
The effective protogenic groups triazole and tetrazole can ammonium-biphosphate ion pairs (QAPOH) with higher PA
act as proton carriers in PEMs to replace water and imidazole interaction energy of 151.7 kcal mol 1 as shown in Scheme 6.
for high-temperature operation. Though the membranes with During the operation of HT-PEMFC, the quaternized PEMs
triazole and tetrazole groups have low PA doping level exhibited high proton conductivity and excellent stability.
(Generally, ADL < 4), these PA doped PEMs exhibit moderate Moreover, during the temperature cycle tests from 80–160 °C,
proton conductivity in a dry state and good electrochemical the single cell voltage remained relatively stable, and no
stability under fuel-cell operation conditions.[51] change was observed in the high frequency resistance (HFR) of
Furthermore, the nitrogenous heterocyclic imidazole,[52]
pyrazole,[53] pyridine[54] and piperidine[55] were introduced into
the main chain or the side chain of the PBIs to increase the
alkaline sites and acid-base interaction, thus the PA absorption
and retention. For example, Quartarone et al. tuned the alkaline
sites of PBI via incorporation of pyridine, bipyridine and
pyrazole groups into the main chain of PBIs. After the PA
removal experiments, the remaining ADL of 4.5 of PA doped
PEMs containing pyridine groups was much higher than that of
the PA doped mPBI membranes (remaining ADL was about 2.0).
This enabled the remaining conductivity of PA doped PBI-5 N-m
membrane two orders of magnitude higher than that of the PA
doped mPBI membrane.[53]
Scheme 6. (a) Quaternary ammonium proton exchange membrane material;

(b) The binder material.

Concept
the cell. This strategy of strong ion pair interactions provides a essential to the application as HT-PEMs based on the interaction
new ideal for the design of molecular structure of HT-PEMs, of ion-pairs.
which is expected to improve the PA retention in the PA-doped
PEMs in the presence of water. In addition, Wang et al.
introduced quaternary ammonium ion groups into PBI main Siphoning effect by using microporous polymers
chain via chemical modification.[57] The proton conductivity and
PA retention of the PEM were improved obviously. The proton As discussed above, the PA doped level can be improved by
conductivity of PBI-Sc-X was stable for 72 h under the increasing the interaction between PA and the functional
conditions of at 80 °C and 40 % RH. However, there are some groups. Another preparation approach is to introduce porosity
outstanding problems in the quaternary ammonium polymers into the PBI by using phase inversion or porogen addition
such as the stabilities of the quaternary ammonium groups and removal.[10e,29,31] The formed porous microstructures improved
the polymer backbone chains during the operation of HT- the acid doping level thus the proton conductivity at high
PEMFCs. Severe chemical degradation and carbonization oc- temperature without extra humidification. However, these
curred in a short time in quaternized PSf and PES PEMs under approaches suffered from the significant mechanical property
the conditions of high temperature and strong acidity. Tang loss due to the excessive swelling, and PA loss along with the
et al. have elucidated the degradation mechanisms of quater- generated water during frequent cold start-ups in the operation
nary ammonium groups and the backbones of the polymers of fuel cell.
using nuclear magnetic resonance (NMR) spectra analysis in Recently, to allow wide operational flexibility over the full
detail.[58] Therefore, the choose of suitable PEM materials with spectrum of temperature and humidity ranges, Tang et al.
stable polymer chains and quaternary ammonium groups is presented an innovative design strategy by using PA-doped
intrinsically ultra-microporous membranes constructed from
rigid and contorted high free volume polymers. As shown in
Figure 5, the intrinsic ultra-micropores of Tröger’s base (TB)
membranes can form interconnected PA channels for fast
proton transport via siphoning effect. The siphoning effect is
what means that the PA molecules can be absorbed into the
ultra-micropores and constrained via the delocalized effect and
acid–base interactions simultaneously thus enabling higher PA
retention. The membranes having an average ultra-micropore
radius of 3.3 Å showed a strong siphoning effect of PA
retention, thus exhibiting more than three orders of magnitude
higher proton conductivity retention than conventional dense
PA-doped polybenzimidazole membranes (PA/PBI) (Figure 6).
Figure 5. Schematic diagram of interconnected sub-nanometer-sized cavities The resulting PEMFCs displayed impressive performance over a
in microporous membranes for rapid and selective proton transport. much broader temperature ranged from 20 to 200 °C and
Figure 6. (a) Chemical structures and 3D view of DMBP-TB modelled structure in an amorphous cell (308 K). (b) i–V curves, power density and HFR of DMBP-
TB/PA MEAs without backpressure or external humidification as a function of operating temperature: 20–200 °C.
Concept
accomplished over 100 start-up/shut-down cycles even at rapid electrodynamics within electrodes and electrolytes, and
20 °C.[59] Therefore, we believe that the siphoning effect of the which is difficult to be poisoned by carbon monoxide (CO). The
intrinsic ultra-microporosity can provide a new idea to improve composite HT-PEM, IHA-S was prepared by Lee et al. via
PA retention and thus enhancing the cell performance. blending silicotungstic acid, tetraethyl silicate complex with
mPBI. Thus, the ADL, proton conductivity and thermal stability
of the HT-PEMs were improved via ionic interaction between
Doping inorganic particles into polymer matrix heteropoly acids and imidazole groups. The proton conductivity
of IHA-S was achieved as high as 206 mS cm 1 at 150 °C without
To improve the mechanical properties, chemical stability and extra humidification, which was much higher than that of pure
ionic conductivity of the membranes, inorganic particles are mPBI. However, to ensure the high proton conductivity, it is still
often added to polymer electrolytes as fillers. In general, there necessary to dope IHA-S membranes with PA.[63] Lu et al.
are two purposes for the addition of inorganic fillers into PBI presented a novel inorganic composite PEM via assembling
based HT-PEMs: (1) to increase PA absorption, thus improving phosphotungstic acid (HPV) nanoparticles into highly ordered
proton conductivity; (2) to reduce PA loss, thus improving fuel mesoporous silica by vacuum-assisted strategy. The proton
cell durability. Pu et al. prepared composite HT-PEM by doping conductivity of the inorganic composited PEM was 45 mS cm 1
nano-silica particles into PBI matrix.[60] It was found that the PA at 150 °C, and the peak power density of 90 mW cm 2 for the
loss gradually decreased with the increased silica content in the corresponding single cell was achieved in HT-PEMFC using
PEM via the PA leaching tests, which may be caused by the methanol/oxygen as fuel.[64] Thus, the problem of PA loss may
adsorption of PA on the surface of silica. However, the simple be solved fundamentally by the application of heteropoly acid
doping method couldn’t improve the cell performance instead of PA. However, at present, the low proton conductivity
effectively.[54b,61] Mustarelli et al. prepared composite HT-PEMs and power output are still difficult to meet the practical
by recombining PBI with imidazole modified silica.[61] The application requirements of HT-PEMFC, thus leading to a great
modified particles had a good chemical compatibility with PBI restriction of further large-scale applications.
as well as a high basicity with a pKa value of about 14. After PA
removal experiments, the proton conductivity of the composite
membrane was 3 orders of magnitude higher than that of pure Other strategies
PBI membrane. Recently, a novel SiO2/c-PBI composite mem-
branes were prepared by using BIM-Cl with imidazole units as a There are many efforts carried out focusing on the methods of
new cross-linker and investigated for HT-PEMs. The mechanical solving the PA loss, and obvious successes have been achieved.
strength, PA uptake (i. e., conductivity) and PA retention of the Some researchers tried to limit PA in the inner layer by making
composite PBI membranes were simultaneously enhanced by sandwich-type membranes. For example, the voltage decay
the incorporation of hygroscopicity SiO2 nanoparticles via an rates of the cells with three-layered membranes were much less
improved equilibrium partition composition of PA and water, as than that of the cells with single-layered membranes in long-life
the third acid loss mechanism proposed by Kim et al. Thus, the time tests of about 1000 h.[65] However, at present, the methods
c-PBI-20 SiO2-2 membrane based H2 O2 HT-PEMFC exhibited a to reduce the PA loss mainly focus on the modification of PEMs,
peak power density of 497 mW cm 2 with no extra humidifica- there is few studies focusing on the catalyst layer and gas
tion at 160 °C due to the high proton conductivity.[62] Therefore, diffusion layers of the electrodes. To improve the PA retention
the study of the influence of inorganic fillers on the PA doped in the electrodes which was migrated from the PA doped
membranes is of great significance to the large-scale produc- membrane, a small amount (6 wt%) of aluminum oxide (Al2O3)
tion and industrialization of PBI ionic membranes in the future. was added into the catalytic layer by Oh et al.[66] The addition of
Al2O3 was beneficial to improve the durability of fuel cells due
to the production of Al(H2PO4)3, which not only reduced the PA
Replacing PA with solid acid loss, but also increased the electrochemical area of the catalyst.
Therefore, this research provides a new strategy to reduce the
Heteropoly acids which are composed of hetero atoms and PA loss in the HT-PEMFC based on PA doped PEM.
polyatoms linked by oxygen atoms coordination bridges in a
certain structure, are a kind of oxygen-containing polyacids and
have high catalytic activity and oxidation reducibility. Common Conclusions
solid heteropoly acid compounds such as silicotungstic acid
and phosphotungstic acid are consisted of heteropoly anions, There is much research on HT-PEMFC at present, but its
cations (protons, metal cations, organic cations) and water or industrialization is still in the primary stage. Compared with the
organic molecules. By creating pathways for water molecules, commercial LT-PEMFC based on perfluorosulfonic acid (PFSA)
the inorganic heteropoly acids can decrease the electroosmotic membrane, there is still a long way to go. One big challenge for
resistance effectively, and maintain the proton conductivity as PA doped PEMs is the PA loss under complicated practical
much as possible. These inorganic materials can increase the operation environments. In this concept, we summarize the
ADL of the polymer membranes and thus improving the proton latest developments of the strategies to reduce the PA loss
conductivity. Silicotungstic acid (H4[W12SiO40]·nH2O) exhibits a systematically. It is believed that the PA loss can be fundamen-
Concept
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Chemistry—A European Journal doi.org/10.1002/chem.202202064

Phosphoric-Acid Retention in High-Temperature Proton-

Chem. Eur. J. 2022, 28, e202202064 (1 of 13) © 2022 Wiley-VCH GmbH

Introduction with a PEM, which include the electrodes, electrolyte, catalyst,

Chem. Eur. J. 2022, 28, e202202064 (2 of 13) © 2022 Wiley-VCH GmbH

Chem. Eur. J. 2022, 28, e202202064 (3 of 13) © 2022 Wiley-VCH GmbH

dissociate to provide the protonated product of phosphacidium PA evaporation

PA leaching out along with water

Mori et al. found that phosphoric acid in the PA-doped PEM

Chem. Eur. J. 2022, 28, e202202064 (4 of 13) © 2022 Wiley-VCH GmbH

Complex equilibrium mechanism of PA and water The approaches to reduce PA loss

Chem. Eur. J. 2022, 28, e202202064 (5 of 13) © 2022 Wiley-VCH GmbH

Figure 4. The main approaches to reduce PA loss in PA doped PEMFCs.

anhydrous proton conductivity of phosphonated polymers at

Chem. Eur. J. 2022, 28, e202202064 (6 of 13) © 2022 Wiley-VCH GmbH

Chem. Eur. J. 2022, 28, e202202064 (7 of 13) © 2022 Wiley-VCH GmbH

Scheme 3. Synthesis of phosphonic acid PPSU (P-PPSU), x is value of PD.

Chem. Eur. J. 2022, 28, e202202064 (8 of 13) © 2022 Wiley-VCH GmbH

Scheme 5. The main structures of pyridine-containing aromatic polyether.

Scheme 6. (a) Quaternary ammonium proton exchange membrane material;

Chem. Eur. J. 2022, 28, e202202064 (9 of 13) © 2022 Wiley-VCH GmbH

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