Journal of Power Sources 533 (2022) 231386

Contents lists available at ScienceDirect

Journal of Power Sources

journal homepage: www.elsevier.com/locate/jpowsour

Review article

Proton exchange membranes for high temperature proton exchange

membrane fuel cells: Challenges and perspectives
Erli Qu a, 1, Xiaofeng Hao a, 1, Min Xiao a, Dongmei Han a, b, Sheng Huang a, Zhiheng Huang a,
Shuanjin Wang a, *, Yuezhong Meng a, **
a
The Key Laboratory of Low-carbon Chemistry & Energy Conservation of Guangdong Province, State Key Laboratory of Optoelectronic Materials and Technologies,
School of Materials Science and Engineering, Sun Yat-sen University, Guangzhou, 510275, PR China
b
School of Chemical Engineering and Technology, Sun Yat-sen University, Zhuhai, 519000, PR China

H I G H L I G H T S

• Influences of structure for membrane on single cell performance are analyzed.

• Four categories of high temperature proton exchange membranes are summarized.
• Advantages and drawbacks for proton exchange membranes are contrasted.
• Suggestions of future development for proton exchange membranes are discussed.

A R T I C L E I N F O A B S T R A C T

Keywords: Proton exchange membranes (PEMs) have received immense attentions for their core roles in high temperature
High temperature proton exchange membrane proton exchange membrane fuel cells (HT-PEMFCs). For a high-performance polymer electrolyte, stable me­
fuel cell chanical property and high proton conductivity on the order of 10− 2 S cm− 1 at low humidity (or anhydrous
Proton exchange membrane
conditions) and high temperature are ultimately necessary. With emphasis on this practical principle, phosphoric
Acid doping
acid doped polybenzimidazoles (PBIs) have become one of the hottest materials in the field of proton conducting
Polybenzimidazoles
Non-polybenzimidazole membrane that exhibit high proton conductivity with values closing to 10− 2 S cm− 1. In addition to PBI, non-PBI
based proton conducting polymers that exhibit satisfactory conductivity and intrinsic mechanical stability are
also exciting research in HT-PEMs. This review summarizes the recent progresses in the HT-PEMs, and addresses
the challenges and promising directions for further development of HT-PEMs.

by way of water splitting, which can output hydrogen for further

1. Introduction
Combustion of fossil fuel has led to the deterioration of the global
environment, which is mainly due to the massive emission of carbon
dioxide (CO2). With the aggravation of environmental pollution and
traditional energy shortage, seeking green and clean renewable energy
and efficient energy conversion technology are arduous tasks in the 21st
century [1–5]. In order to obtain sustainable energy cycle, an effective
strategy is to research a credible energy carrier for the storage of
intermittent renewable energy for human utilization [6–9]. In this
respect, a typical example is the conversion of the solar to hydrogen fuel
application in fuel cells [10–12].
Fuel cell is a clean and highly efficient energy technology which can
directly convert chemical energy of fuel into electrical energy, and it is
mainly composed of anode, cathode and electrolyte. Among them,
proton exchange membrane is the core component of fuel cell, which
serves as a solid electrolyte to provide ion transfer and prevents fuel
from penetrating between electrodes and will directly affects the per­
formance and lifespan of fuel cell [13–18]. According to different clas­
sification criteria, fuel cells can be divided into many types. Based on the
types of electrolyte membrane materials, fuel cell can be divided into six
categories: proton exchange membrane fuel cells (PEMFCs), anion

* Corresponding author.
** Corresponding author.
E-mail addresses: wangshj@mail.sysu.edu.cn (S. Wang), mengyzh@mail.sysu.edu.cn (Y. Meng).
1
Erli Qu and Xiao-feng Hao contribute equally to this work.

https://doi.org/10.1016/j.jpowsour.2022.231386
Received 27 August 2021; Received in revised form 18 March 2022; Accepted 29 March 2022
Available online 7 April 2022
0378-7753/© 2022 Elsevier B.V. All rights reserved.
E. Qu et al. Journal of Power Sources 533 (2022) 231386

Glossary of abbreviation ILs ionic liquids

TAB tetraaminobiphenyl
Abbreviation Description IPA isophthalic acid
HT-PEMFC High-temperature proton exchange membrane fuel cell PPA polyphosphoric acid
LT-PEMFC Low-temperature proton exchange membrane fuel cell P2O5 phosphorus pentoxide
PEMFC proton exchange membrane fuel cell ADL acid doping level
PEM proton exchange membrane Tg glass transition temperature
PBI polybenzimidazole p-PBI poly[2,2’-(p-phenylene)-5,5′ -bibenzimidazole]
PA Phosphoric acid AB-PBI poly(2,5-benzimidazole)
m-PBI Poly[(2,2’-(m-phenylene)-5,5’-(bibenzimidazole)/meta- CsH2PO4 cesium dihydrogen phosphate
polybenzimidazole] SPEEK sulfonated poly(ether ether ketone)
PFSA Perfluorosulfonic acid CsHSO4 cesium hydrogen sulfate
USDOE United States Department of Energy POSS polyhedral oligomeric silsesquioxane
AEMFC anion exchange membrane fuel cell PAA polyacrylic acid
PTFE Polytetrafluoroethylene MOFs metal organic frameworks
PAEK Poly(arylether ketone) CNTs carbon nano-tubes
SPI sulphonated polyimide GO graphene oxide
PPO Poly(phenylene oxide) PVPA Poly(vinyl phosphonic acid)
MEA membrane electrode assembly PVDF polyvinylidene fluoride
IEC Ion Exchange Capability MWCNT Multiwalled carbon nano-tube
OPBI Poly[2,2′ -(p-oxydiphenylene)-5,5′ -bibenzimidazole] PVP polymer polyvinylpyrrolidone
PES polyether sulfone GDL Gas diffusion layer
PILs polymer ionic liquids

exchange membrane fuel cells (AEMFC), molten carbonate fuel cell
(MCFC), phosphoric acid fuel cell (PAFC), solid oxide fuel l cell (SOFC)
and direct methanol fuel cell (DMFC) [19–21]. Compared with other
energy conversion devices [22–25], PEMFCs have lots of outstanding
properties, such as high efficiency at wide range temperature, compact
construction, sustained operation at a wide current density, the potential
for low cost and volume, long stack life, fast start-ups and suitability for
wide temperature operation [26]. Therefore, PEMFCs are regarded as
one of the most promising electrochemical technologies for sustainable
power generation throughout the world.
The basic working principle of PEMFCs is shown in Fig. 1. The
hydrogen split into electrons and H+ at the anode of FCs through
oxidation reaction. Then, O2 combines with electrons and H+ through a
Fig. 1. Schematic diagram of a PEMFC.
reduction reaction at the cathode. Clearly, for both side reactions to
happening continuously, electrons produced from H2 must travel across
an external circuit to the cathode.
As shown in Fig. 2a, a conventional PEMFC primarily consists of
bipolar plates with channels machined, a membrane electrode assembly
(MEA) containing PEMs, the catalyst layers and porous gas diffusion
layers [27]. For PEMFCs, according to the different operating temper­
ature, it can be classified into two types, low temperature (below 80 ◦ C)
PEMFCs (LT-PEMFCs) and high temperature (high than 120 ◦ C) PEMFCs
(HT-PEMFCs). The spider plots in Fig. 2b outline the differences between
HT-PEMFCs and LT-PEMFCs. Compared with LT-PEMFCs, HT-PEMFCs
are a clean energy conversion device with the advantages of increasing
oxygen reduction reaction kinetics, reducing CO poisoning, and
simplifying water/heat management and cooling system [28–33].
However, with increasing operating temperature, HT-PEMFCs will face
more technical challenges compared with LT-PEMFCs. For example, the
cost of system, startup time of high temperature and security of
HT-PEMFCs. As a matter of fact, traditional membranes such as Nafion
and sulfonated membranes are unstable at higher temperature, which
can not be used as HT-PEMs. By employing phosphoric acid (PA) as an
proton carrier, PA doped PBI based membranes were used as HT-PEMs,
which can afford comparative proton conductivity at high temperature
but resulted in a large ohmic increase of MEA due to the transport
mechanism of H+ in the membrane and its thickness, thereby reducing
the cell voltage, power and efficiency of MEA under a constant current
[17,34]. Therefore, there is still a long way for commercialization of
HT-PEMFCs.
More importantly, MEA is the heart of PEMFCs that comprising
multistep procedure to fabricate. For MEA of HT-PEMFCs, the desirable
performance is established on the balance between mechanical stability
and electrochemical property of PEMs. Therefore, the influencing fac­
tors on the performance of HT-PEMs need to be considered. In order to
achieve desirable performance for HT-PEMFCs, PEM in this system
should meet the following requirement: low material cost, high proton
conductivity, good chemical stability and excellent mechanical strength;
besides, long durability. The spider plots in Fig. 2c summarize state-of-
art factors of HT-PEMs. Meanwhile, the high proton conductivity at high
temperature is the key to obtain high power density for HT-PEMFCs.
Along with dehydration of the traditional membrane under high

2
E. Qu et al. Journal of Power Sources 533 (2022) 231386

Fig. 2. (a) Typical PEMFCs structure, (b) contrast between HT-PEMFCs and LT-PEMFCs, (c) property spider charts of HT-PEMs.

temperature, the proton conductivity would decrease correspondingly,
and then limits the performance of HT-PEMs.
According to 2017 cost-analysis (Fig. 3) [35], the cost of an
80-kWnet (Net Electric Power) HT-PEMFCs system project directly using
hydrogen is estimated to be $45/kWnet when the output is 500000
units/year, while the cost of membrane is about 9% ($4.05/kW). Ac­
cording to the present technology, the goal cost of vehicles PEMFC in
2020 is about $40/kWnet, suggesting the cost of the membrane will be
reduced by $0.45/kW. In order to maintain the long-term competitive­
ness of the existing technologies, the system cost must be further
reduced to ultimate $30/kW net, which is equivalent to $1.35/kW
reduction for membrane cost in high-volume markets. Therefore, in
order to achieve excellent performance for HT-PEMFCs, PEM in this
system should meet the following requirement: high proton
conductivity, good chemical stability and excellent mechanical strength;
besides, long durability.
Therefore, the design and development of neoteric material with
above properties at elevated temperatures and low humidification is the
focus and hotspots during the development of HT-PEMFCs. Up to now, a
series of PEMs has been prepared and applied in HT-PEMFCs. In recent
years, we notice that most related reviews have been published which
focused on PBI-based membrane. Moreover, a few previous references
have reviewed only part of PBI membrane and the functionalization of
PBI at elevated temperature (>100 ◦ C). However, the review article that
comprehensively generalizes the types and related preparation methods
and properties of PEM material for HT-PEMFC is still lacking. As-
prepared membrane can be divided into the following four groups in
Fig. 4.

Fig. 3. (a) Cost analysis for an 80 kWnet vehicle PEMFC system with the output of 100,000 and 500,000 units/year; (b) breakdown of the 2017 projected fuel cell
stack cost at 500,000 units/year [35].

3
E. Qu et al.
Fig. 4. Proton exchange membranes for HT-PEMFCs.
The purpose of this review is to summarize the recent development
on HT-PEMs. This review focuses on the types, preparation methods,
possible proton conducting dopants, and properties of PBI and non-PBI
based membranes. At the same time, a future research directions and
possible approaches for HT-PEMs will be discussed. The content plan is
as follows: (1) a brief introduction about PEM as the main part of HT-
PEMFC in section 1; (2) PBI-based HT-PEMs; (3) aromatic polymer
based HT-PEMs; (4) composite membranes for HT-PEMs; (5) fluorinated
polymer for HT-PEMs.
2. PBI-based HT-PEMs
2.1. Proton conduction mechanism and membrane preparation methods
PBI is an aromatic linear heterocyclic rigid semi-crystalline polymer
containing repeated benzimidazole units, and it owns excellent chemical
resistance, high mechanical strength, good moisture regain and thermo-
oxidative stability above 80 ◦ C [36,37]. Owning to the above advantages
as well as the special alkaline structure of the benzimidazole rings, PBI is
a candidate material for HT-PEMFCs, which can be acted as both proton
donor(acidic) and acceptor(basic). However, the intrinsic proton con­
ductivity of PBI is very low, only 10− 9 mS cm− 1, that is, insulation
property, which cannot be used as an independent solid electrolyte [38].
As we know, acid-base complex polymer system constituted by means of
reacting basic sites with strong acids is a kind of PEMs. PBI can be doped
by many different inorganic acids to enhance the proton conductivity
[39–42]. Previous studies have implied that those acids may be doped in
the polymer including HCl, HNO3, H3PO4, HClO4 and H2SO4, etc.
Among these acids, the achievable conductivity is H2SO4 > H3PO4 >
HClO4 > HNO3 > HCl [43–47]. After being protonated by acid, PBI can
be used as a conductor to transport protons. For a high-performance
4
Journal of Power Sources 533 (2022) 231386
HT-PEM, high proton conductivity is necessary under anhydrous con­
ditions and at high temperature. Although, H2SO4 is the acid that leads
to the maximum conductivity, finally, the acid chosen is H3PO4 (phos­
phoric acid; PA) [48], because H2SO4 doped PBI membrane still require
relative humidity greater than 50% to meet this performance and its
poor stability at elevated temperatures, whereas investigations have
discovered that PA is a good electrolyte with high thermal stability and
its proton conductivity is as high as 800 mS cm− 1 at 200 ◦ C [49], and it
can still maintain high proton conductivity even in the absence of water.
So, for HT-PEMFCs, the PA doped PBI polymer membrane could be
capable of operating under anhydrous condition at temperatures up to
200 ◦ C due to the presence of PA which acts as the proton carrier [50,
51]. Savinell et al. [52] [][][]were the first to employ PA doped PBI,
as-obtained membrane which delivered excellent proton conductivity
above 100 ◦ C.
In addition, PA doped PBI has some other advantages, that is, low
vapor pressure at high temperature and significantly lower cost than
perfluorosulfonic acid (PFSA) PEM. Moreover, PA doped PBI is the only
membrane which is in accordance with the high temperature membrane
standard of United States Department of Energy (USDOE) so far. At
present, it is generally believed that the proton conduction in PBI
membrane doped with PA is mainly carried out through the hopping
mechanism of Grotthus as shown in Fig. 5a [53].
Grotthus mechanism is a proton transition mechanism proposed by
Von Grotthus. When a proton reaches a water molecule and temporarily
becomes a H3O+, and another different proton separates from the same
H3O+ into the next transition. In the presence of PA, a similar mecha­
nism is observed in the Grotthus chain between PA and ion pairs
H4PO4+/H2PO4− . This mechanism permits proton conductivity along
with the only water for the system is produced by the cathode. For PA
doped PBI membranes, the proton conductivity is expected to be lower
E. Qu et al.
Fig. 5. Proton conduction mechanisms of (a) PA-doped PBI [53] and (b) in pure PA [54].
than that of liquid PA, because the polymer partially breaks the Grottus
chain in this case. In addition, the pure liquid PA has the highest intrinsic
proton conductivity in any known substance. Ma et al. [55] and
Authayanun et al. [56] proposed the following equation for the con­
duction mechanism of structural diffusion (Grottus mechanism).
Anode : H2 PO−4 + H + ⇌H3 PO4 (1)
Membrane : H3 PO4 + PBI⇌H2 PO−4 + PBI⋅H + (2)
(Or H3 PO4 + H2 O⇌ H2 PO−4 + H3 O+
Cathode : PBI ⋅ H + ⇌PBI + H + (3)
Researches show that, at low PA concentration, the hopping Grotthus
mechanism is the main transformation between H3O+ and H2O, while at
high PA concentration, the hopping number of protons increased be­
tween H4PO4+ and H3PO4 molecules, considerably increasing its proton
conductivity [56,57].
Additionally, recent research [54] on the proton conduction mech­
anism in pure PA has revealed the reason for the high proton conduc­
tivity in PA. The basic steps of proton conduction, proton transfer and
structure reorganization were realized by waving and relatively weak
hydrogen bonds. But PA has a high density and very strong hydrogen
bond, which generally results in an ordered structure with very slow
proton dynamics. Nevertheless, the current work delivers an explicit
explanation: both weak solvent interaction and sufficient disorder (e.g.,
configuration resistance) can explain the high concentration and
mobility of proton carriers (Fig. 5b), leading to high proton conductivity
at the anhydrous condition.
In 1995, Wainright et al. [58] firstly proposed to use PBI based
membrane in fuel cell. The contention for this invention is that
Nafion-based LT-PEMs have a high electroosmotic resistance value,
which limits its application under humidified conditions and below
100 ◦ C, making water management system and operation of hydrogen
reforming containing impurities carbon monoxide (CO) and CO2 diffi­
cult. After that, PA doped PBI membrane has become the main focus of
researchers for many years. Usually, low PA doping level has little effect
on proton conductivity, in turn, high PA doping level considerably in­
creases its proton conductivity but at the cost of sacrificing mechanical
stability due to the strong plasticization of PA at high temperatures,
which hampers its practical application in HT-PEMFCs [59,60]. So,
more and more attention has been paid to prepare PBI membrane with
good mechanical properties and high PA doping level for HT-PEMFCs
[61–64].
At present, m-PBI (poly[(2,2’-(m-phenylene)-5,5’-(bibenzimida­
zole)]) is still the only commercial PBI, and the preparation of m-PBI can
5
Journal of Power Sources 533 (2022) 231386
be divided into two dominating approaches: melt polymerization and
solution polymerization. For melt polymerization, that is heterogeneous
synthesis, it includes one-step and two-step methods. In 1961, Vogel and
Marvel [65] first reported a two-step preparation procedure of m-PBI
through condensation polymerization between quaternary amines and
binary ester. Afterwards, in order to simplify the synthesis procedure,
Choe [66] designed a one-step method to obtain high molecular weight
m-PBI by using tetraaminobiphenyl (TAB) and isophthalic acid (IPA) as
monomers in the presence of a catalyst. The other method of preparing
PBI is to utilize homogeneous solutions containing solvents such as
polyphosphoric acid (PPA) [67]. For this, there are a large number of
acidic solvents and multistage separation procedures, but it is an effec­
tive method to synthesis high molecular weight polymers in laboratory
at mild temperature (170–200 ◦ C) and more stable monomers, that is,
tetrahydrochloride stabilized TAB. Besides PPA, other solvents can also
be employed to synthesize PBI in homogeneous solutions. Eaton et al.
[68] proposed that the low viscosity mixture liquid with meth­
anesulfonic acid (MSA) and phosphorus pentoxide(P2O5) could be used
as a mixed solvent for homogeneous synthesis and subsequent pickling.
The synthesis process of the above two methods is shown in Fig. S1
(supplementary information).
2.2. Modification of main chain structure
Currently, m-PBI is a main type of PBI membrane for HT-PEMs after
PA doping. Due to the strong rigidity of PBI main chain and hydrogen
bonds formed via the N–H bond of imidazole ring, the intermolecular
interaction force is very strong, which results in poor solubility and
processing formability, and then, limits application of PA-PBI membrane
in the field of HT-PEMFCs [69–71]. Li et al. [64] reported that the
polymer chain of m-PBI was closely related to intermolecular hydrogen
bond, the polymer had a high glass transition temperature (Tg), so m-PBI
was only partially soluble in selected polar aprotic solvents at a rela­
tively low concentration. As we know, the diverse chemical structures
can bring about various properties in reference to functionalities, so the
research and development of neoteric PBI structure material is an
effective way to expand the research scope and further improve the
performance of PA-PBI membrane system. This kind of modification is
mainly carried out by increasing the number of basic groups, intro­
ducing flexible bonds and sulfonic groups in the main chain of PBI.
In view of foregoing circumstances, many benzimidazole based
polymers with main chain modification, such as p-PBI [72,73], poly(2,
5-benzimidazole) (ABPBI) [74,75], pyridine containing PBIs (Py-PBI
or PBI-5N) [76–78], poly[2,2′ -(p-oxydiphenylene)-5,5′ -bibenzimida­
zole](OPBI) [79–81], PBIOO [82,83], tert-butyl PBI [84], sulfonated PBI
(s-PBI) [85,86] and Pm-b-On-PBI [87], were intensively prepared,
E. Qu et al.
studied and applied in HT-PEMFCs. These PBI derivatives structures of
main chain modification has been summarized in Table 1.
Since p-PBI was first prepared in the early 1960s, it has attracted
more and more researchers’ attention. For example, Sannigrahi et al.
[88] pointed out that p-PBI had excellent tensile strength and stiffness,
but, its glass transition temperature was lower (361 ◦ C) than that of
m-PBI (420 ◦ C), implying the flexibility was improved by introducing
the p-phenylene link to the backbone.
Compared to m-PBI, ABPBI presents a simpler structure in the
absence of the connecting phenyl rings, so there is a high concentration
of the basic sites in the structure. ABPBI has been investigated to doped
with PA for HT-PEM by Kim et al. [89], Litt et al. [40] and Krishnan et al.
[90]. The relevant results suggested that ABPBI could absorb much more
PA than PBI in the same conditions. At the same time, compared to PBI,
the monomer of ABPBI can be produced easily. Moreover, ABPBI ex­
hibits a higher affinity to acids than PBI, allowing for doping with PA
and sulfonated by H2SO4.
Increasing the numbers of N atoms or NH groups on the main chain
of PBI can improve the affinity of matrix to acid molecules, thus
improving the acid doping level (ADL) and proton conductivity of PBI
membrane. Pyridine groups were usually added to the PBI backbone as
an additional nitrogen-containing aromatic heterocyclic ring to increase
the content of basic groups in the polymer while maintaining its
inherently high thermal oxidation stability. For Py-PBI, Xiao et al. [91]
discovered that the solubility of the polymer were enhanced after the
benzene ring was replaced by a pyridine ring. Moreover, Kallitsis and
Table 1
PBI derivatives structures of main chain modification.
Name Structure
p-PBI
ABPBI
Py-PBI
OPBI
PBIOO
tert-butyl PBI
s-PBI
P0.5-b-O0.5-PBI
6
Journal of Power Sources 533 (2022) 231386
Geormezi [92] also proposed an aromatic copolymer membrane with
polar pyridine groups in the main chain, and the antioxidation stability
of membrane was enhanced.
The groups ether, sulphone, etc. also have an important effect on the
properties of the polymer. Studies demonstrated these groups reduced
the thermal oxidation stability, but enhanced the solubility and flexi­
bility of the polymer [93]. For OPBI and PBIOO, the solubility of PBI in
organic solvent increased by introducing aromatic ether bond into the
main chain [94]. In fact, the ultimate practicability of the HT-PEMs
depends on a variety of factors, such as proton conductivity, mechani­
cal properties and cycle life, etc., all of which must reach a certain index
to meet the use requirements. However, a single monomer is unable to
take into account the balance various properties. Through the
co-polymerization of several monomers with different function groups, a
variety of function groups can be introduced into the polymer matrix, so
as to achieve the balance among various properties and obtain a mem­
brane with satisfactory comprehensive performance. Therefore, the
copolymerization has become an important means to improve the
comprehensive performance of PBI [95]. Due to the different physical
and chemical properties of different blocks, block copolymer mem­
branes can form a nano-phase separation structure in the membrane,
resulting in a continuous ion nano-channel that is conducive to proton
transport.
For Pm-b-On-PBI [87], actually, the modification of main chain
structure belongs to making block copolymer, which has been investi­
gated for HT-PEMs. Due to the combination of rigid and flexible
Ref
[73]
[75]
[78]
[81]
[83]
[84]
[86]
[87]
E. Qu et al.
segments of the copolymer, the block copolymer membranes show
obvious nano-phase-separated structures, which afford continuous ion
nanometer channels for high proton conducting ability. As the results,
the MEA obtained using Pm-b-On-PBI polymer achieved a maximum
power density of 360 mW cm− 2 at 160 ◦ C under hydrous conditions,
which was much better than those of traditional linear p-PBI (250 mW
cm− 2) and OPBI membranes (268 mW cm− 2) (Fig. S2 in supplementary
information).
Sulfonation is also one of the hot spots to modify PBI backbone.
Generally speaking, the introduction of sulfonic groups helps to improve
the conductivity of the membranes [96,97]. Sensio et al. [98] prepared
sulfonated ABPBI membrane (Fig. S3 in supplementary information)
with 35–49% of sulfonation degree. The PA doping level of these
membranes increased with the increase of sulfonation degree. When the
sulfonation degree was 41%, the doping level was 4.6, and the sulfo­
nated ABPBI membrane had the highest conductivity of 0.035 S cm− 1 at
185 ◦ C in anhydrous condition.
Angioni et al. [99] prepared aryloxy-based PBIs using co-monomers
with 100% mono- and di-sulfonation (Fig. S4 in supplementary infor­
mation). The conductivity of mono-sulfonated PBI was about 0.1 S cm− 1
at 120 ◦ C and 50% RH. Compared to the mono-sulfonated polymer,
di-sulfonation was efficient only at lower ADLs, which allowed a further
2–3 times higher proton conductivity under similar ADLs.
As we know, the membranes with high sulfonation degree tend to
have low mechanical strength and serious swelling, and their proton
conduction is still dependent on water to a certain extent [100]. For
example, there are many literatures trying to dope the sulfonated PBI
membrane with PA and control the degree of sulfonation, which have
achieved certain results. Angioni et al. [101] prepared PBI with different
sulfonation degrees by using different sulfonic acid monomers (Fig. S5a
in supplementary information), and the corresponding electrolyte
membranes were obtained via doping the pristine polymers in solutions
using different PA concentrations. The results showed that the sulfo­
nated membrane had higher conductivity than the initial membrane at a
certain sulfonation degree under the same content of PA solution at
120 ◦ C and 50% RH, while at a higher sulfonation degree, these prop­
erties decreased (Fig. S5b in supplementary information). Furthermore,
the single cell performances were tested for sulfonated PBI membranes
at 150 ◦ C without external humidification using H2 and air as the
reactant gases. The OCV was above 0.9 V, and power density was about
320 mW cm− 2, irrespective of the number of sulfonic groups, indicating
these materials are promising as membranes for HT-PEMFCs (Fig. S5c in
supplementary information).
Nicotera et al. [102] proposed that the formation of ionic
cross-linking network between the multi sulfonic groups reduced the
mobility of protons (Fig. S6 in supplementary information), the single
sulfonated PBI membrane had higher ADL and proton conductivity
when doping the same PA concentration (Table 2). This feature is ex­
pected to solve the mutual restriction between high ADL and long-term
stability of PA-PBI membrane system.
2.3. Modification of side chain
During the investigation of PEMs, the researchers found that when
the ionic group was located on the side chain of polymer and far away
from the main chain of polymerization, the polymer had better
Table 2
Doping levels (N) and conductivity values for the two membranes activated with 50% and 70% PA aqueous solution a [102].
sample 50% PA aqueous solution
− 1
N δ 120 C-0% RH (mS cm
◦
) δ 120 C-50% RH (mS cm
◦
PBI-5N 7.3 5 29
2Θ-PBI-1SO3H 7 2 21
2Θ-PBI-2SO3H 4.5 1 16
a
Values obtained at 120 ◦ C and 0% and 50% RH.
7
Journal of Power Sources 533 (2022) 231386
dimensional stability and higher proton conductivity [103,104], and the
results are dependent on an obvious phase separation structure was
formed in the polymer under this state. And then, this molecular design
method can also be applied to the molecular design of HT-PEMs so as to
enhance the material desirable properties.
The –NH– group on benzimidazole ring is the chemical active group
of PBI polymer, and specific functional groups can be grafted into the
side chain of PBI polymer through N-substitution reaction, thus
improving the properties of PBI polymer.
Lin et al. [105] synthesized butylsulfonate grafted
polybenzimidazole(PBI-BS). Since the grafted PBI had low mechanical
strength, it was blended with pure PBI to prepare PBI/PBI-BS blend
membranes. The introduction of bulk side chains made the sulfonated
membrane produce larger free volume for acid storage. For example, the
conductivity of PA doped PBIh (Mw = 160 k Da) membrane was 1.44 ×
10− 2 S cm− 1 at 160 ◦ C and anhydrous state, and the PA doped PBIh-BS
membranes and PBIh/PBIh-BS64 blend membranes were 2.30 × 10− 2 S
cm− 1 and 3.12 × 10− 2 S cm− 1, respectively. Compared with near PBI
and PBIh-BS membranes, the PBIh/PBIh-BS blend membranes had better
mechanical properties, ADL, proton conductivity and fuel cell
performance.
Yang et al. [106] prepared benzimidazole grafted PBI (Fig. S7 in
supplementary information), which showed good membrane-forming
property and excellent tensile strength. The tensile strength of PA-PBI
was 16 MPa at room temperature with an ADL of 13.1. The side benz­
imidazole groups provided additional basic sites for the acid-base
interaction onto the PBI macromolecular chain and could enable the
membrane to obtain higher ADL and proton conductivity without
sacrificing mechanical strength. The PBI membrane showed a high
conductivity of 0.15 S cm− 1 with a grafting degree of 5.3% and an ADL
of 13.1. Besides, a H2/air fuel cell based on the membrane exhibited the
peak power density of 351 mW cm− 2 at 160 ◦ C without humidification,
demonstrating it could be utilized as the electrolyte for the HT-PEMFCs.
Wang et al. [107] prepared ethyl phosphoric acid (EPA) grafted
amino-modified PBI (PBI–NH2-EPA-X, X: EPA content) (Fig. S8 in sup­
plementary information). The grafted ethyl phosphonic acid groups
could reduce the leakage of PA to some extent. By introducing EPA into
the matrix so as to enhance the ADL and proton conductivity of the
membranes. Compared to the pristine PBI membranes, as-resulted
membranes presented good long-term stability, dimensional and ther­
mal stability. In particular, the most prominent part is the long-term
stability of PBI-NH2-EPA-X membranes was enhanced, in which the
ADL of pristine PBI membrane was 47.85% much lower than that of the
obtained PBI-NH2-EPA-20 after 240 h. Furthermore, the proton con­
ductivity of PBI-NH2-EPA-15 was 0.062 S cm− 1 at 170 ◦ C, which was
342% much higher than that of the pristine PBI membranes.
2.4. Cross-linking modification
The proton conductivity, PA content and mechanical strength of PA/
PBI electrolyte membrane are mutually restricted, for example, the high
PA content is required to obtain high proton conductivities. However,
the high PA doping level will reduce the mechanical strength of the
membrane due to the strong plasticization of PA. So, how to ensure the
high proton conductivity and sufficient mechanical strength simulta­
neously is an urgent problem to be solved. A very effective method is to
70% PA aqueous solution
− 1
) N δ 120 ◦ C-0% RH (mS cm− 1) δ 120 ◦ C-50% RH (mS cm− 1)
12 14 76
11.9 10 72
8.3 7 50
E. Qu et al.
prepare membranes with covalent crosslinked network structure, which
can improve the mechanical properties and dimensional stabilities of the
membranes. In general, the three-dominating classes of crosslinking are
ionic crosslinking (polymer blending or incorporation of inorganic ma­
terials), covalent crosslinking, and mixed ionic-covalent crosslinking.
Different crosslinking methods will also have different effects on the
properties of membranes.
The concept of acid-base blend is based on a mixture of an alkaline
polymer and an acidic one, via proton transfer from the acidic group to
the basic one to produce acid-base, ionic/non-covalent cross-linking
(Fig. S9 in supplementary information), which was proposed by Kerres
et al. [108] Hasiotis et al. [109] first applied this notion to HT-PEMFCs
by combining PBI with sulfonated polysulphone (SPSF), and then doping
it with PA. The conductivity of PBI-SPSF blends (10− 2 S cm− 1) was
higher than that of pure SPSF (10− 3 S cm− 1). Ionic cross-linking of
membranes has also been reported to result in improved thermal sta­
bility and resistance to free radical erosion, compared to pure acidic
polymers [110]. And its ionic conductivity could be changed through
adjusting the molar ratio of acid to base. A new type of acid-base ion
crosslinked membrane using acidic polymer as a macromolecular ion
crosslinking agent with PBI derivatives such as F6-PBI, PBIOO has also
been studied for HT-PEMs [111]. The weight loss of acid-base blends
used in the experiment was less the 8% after 24 h and less than 20% after
144 h in Fenton’s test, which was much lower than that of pristine PBI
and ABPBI with 40% under the same test, indicating those acid-base
blend membranes presented enhanced oxidation stability in Fenton’s
test. This investigate testifies that it is a promising alternative as mem­
brane for HT-PEMFCs.
Another new approach to crosslink PBI was also reported, which
springed from the ionic cross-linked acid-base blend membranes. The
Friedel-Crafts reaction of sulfonic acid groups and electron-rich phenyl
groups took place at the temperature higher than 200 ◦ C, and the co­
valent cross-linking reaction was carried out by chemically stable aro­
matic sulfone bond to the acid base blend components. Recently, p-
xylylene dichloride [112] and divinyl sulfone (DVS) [113] have been
used as covalent cross-linking agent to synthesize cross-linked PBI. The
covalent cross-linked membrane has excellent chemical stability, and
the mechanical strength can be maintained in the range of usage under
the condition of high PA content. The two cross-linking structures are
shown in Fig. S10 (supplementary information). Yang et al. prepared
crosslinked F6-PBI composite membrane [114] via using a polymeric
crosslinker, i.e. chloromethylated polysulfone, and its structure was
shown in Fig. S11 (supplementary information). When the cross-linking
degree was 4.6%, the conductivity was 0.115 S cm− 1 at 160 ◦ C, and the
maximum power density of a single cell was 360 mW cm− 2. Further­
more, for the crosslinked F6-PBI membrane with an ADL of 10.4 mol PA,
the durability tests with a constant current load of 300 mA cm− 2 at
160 ◦ C indicated no conspicuous performance attenuation during a test
period of 3500 h. However, for the m-PBI membranes with an ADL of
11.5 mol PA, it appeared an intermediate failure. After comparison, the
crosslinked membrane exhibited excellent electrochemical
performance.
Besides, other method was to form a PBI structure by exploiting
epoxy compound as a cross-linking agent to generate covalent chain
with the imidazole group. For example, Ngamsantivongsa et al. [115]
prepared crosslinked ethyl phosphoric acid grafted polybenzimidazole
and polybenzimidazole blend membranes (PBI-EPA/PBI) via blending
epoxy resin as a crosslinker. Compared to pure PBI, PBI containing
epoxide blend (PBI/EP) showed the highest maximum tensile stress
(97.5 MPa) among the blends, and PBI/PBI-EPA/EP blends exhibited
outstanding performances in the case of ADL about 430 wt% and the
proton conductivity of 0.081 S cm− 1 at 160 ◦ C & 0% RH, indicating that
the addition of crosslinking agent such as epoxide improved the relevant
performance of the neat-PBI membrane. Han et al. [116] prepared a
series of covalent cross-linked PBI membrane with excellent thermal,
chemical stability and mechanical strength by utilizing the
8
Journal of Power Sources 533 (2022) 231386
characteristic mechanism of imidazole cured epoxy resin (Fig. S12 in
supplementary information), where 4,4′ -diglycidyl(3,3′ ,5,5′ -tetrame­
thylbiphenyl) epoxy resin (TMBP) as the cross-linker. It is interesting to
note that the proton conductivity of the PA-PBI-TMBP 20% membrane
which was immersed in 14.6 M PA solution at 90 ◦ C for 4 days was also
tested, and it exhibited a high level of 9 mS cm− 1 at 150 ◦ C. The
investigation of proton conductivity stability using the oxidation test is
important t for the durability of HT-PEMFCs.
Generally speaking, the thermostability of the ionic cross-linked
membrane is poor because the ionic crosslinking structure will break
at higher temperature, leading to unacceptable swelling and unstable
mechanical strength [117]. Therefore, in order to overcome this situa­
tion, covalent cross-linked membranes have also been investigated. In
the past few decades, a variety of small molecular and macromolecular
cross-linking agents have been extensively studied for PBI.
As we know, on one hand, the small molecular crosslinker only
contain two or three functional groups. On the contrary, the macro­
molecular crosslinker owns more reactive functional groups, which can
form more crosslinking sites. On the other hand, covalent cross-linking
membranes using small molecular crosslinkers have the tendency of
being brittle after drying. What’s more, most of the crosslinking ap­
proaches will lower the mobility of the polymer chains and are mainly at
the sacrifice of N–H sites on the PBI backbone, thus impeding the ADL
and proton transfer [118]. In view of the importance of the free volume
for acid absorption and the N–H site for proton transfer in the covalent
crosslinking structure, it is an urgent matter to conceive logical polymer
backbone and reasonable crosslinker so as to satisfy the practical of
HT-PEMFCs.
Wang et al. [118] developed a new-type crosslinked PBI without the
sacrifice of effective N–H sites which was based on branched crosslinker
(Fig. S13 in supplementary information). For this PBI membrane, its free
volume and the content of PA absorption can be improved via the
branching structure, and N–H sites can also maintain to proceed effec­
tive proton transfer. The crosslinked membrane presented only a slight
weight loss (<10%) after immersing in Fenton’s reagent at 85 ◦ C for 168
h. Furthermore, the crosslinked membrane delivered enhanced proton
conductivity (73 mS cm− 1, 160 ◦ C & 0% RH), which was better than that
of the linear membrane. Moreover, the maximum peak power density of
690 mW cm− 2 can be obtained for the single cell assembled with the
cross-linked membrane. Durability in terms of OCV, it could be main­
tained for 200 h at a constant current load of 200 mA cm-2 without
degradation. The results implied that the crosslinked branched PBI
membrane at no expense of effective N–H sites could be served as
HT-PEMs.
Li et al. [119] prepared a novel cross-linker PBI membrane to restrain
the reduction of the amount of imidazole groups and improve its me­
chanical stability and proton conductivity (Fig. S14 in supplementary
information). Moreover, the porous polyhydroxy SiO2 nano-particles
were dispersed into the cross-linked PBI membranes (c-PBI-20, 20 rep­
resents the molar percentage of –CH2Cl in the cross-linker to –NH in
Ph-PBI) to fabricate SiO2/c-PBI-x nano-composite membranes (x repre­
sents the percentage of SiO2 nano-particles in the resulting
nano-composite membranes). The c-PBI-20-SiO2-2 membrane shows a
maximum peak power density of 497 mW cm− 2 at 160 ◦ C for H2 and O2
without humidification, which presents comparable or better
HT-PEMFC performance than PA doped m-PBI membrane (442 mW
cm− 2) and PA doped c-PBI-20 (467 mW cm− 2) membrane due to their
superior trade-off between proton conductivity and
dimensional-mechanical stability, and good acid stability. In this way,
the synthesized nano-composite crosslinked PBI membranes are ex­
pected to show enhanced overall performance as HT-PEMs.
Up to now, the crosslinking of PBI is mainly concentrated on amide
type connection, which is related to the reduction of proton sites of ion
conduction (higher PA doping overcame this problem in the above
example). So, more attention should be paid to search new crosslinking
agents and methods. For example, based on PBI and polymer ionic
E. Qu et al.
liquids (PILs) including imidazole ring, the diproton transfer channel
cross-linked membrane was studied by Chen et al. [120]. The difference
between PILs and ionic liquids (ILs) is that PILs trends to establish
continuous ion channels, while owns some unique characteristics of ILs
without IL leakage. The maximum conductivity of [PBI-BuI] [BF4]
cross-linked composite membranes was 0.117 S cm− 1 at 170 ◦ C, and it
could balance the mechanical strength and PA absorption conveys,
allowing it to be a promising candidate for HT-PEMFCs. The preparation
process of [PBI-BuI] [BF4] was shown in Fig. S15 (supplementary
information).
2.5. Introduction of phosphonic acid groups (-PO3H2) on polymer
backbone
It is known to all that the long-term operation PBI based MEAs still
suffer from acid leaching, resulting in the serious attenuation of cell
performance. Therefore, some studies have been carried out to reduce or
eliminate this phenomenon by immobilizing protonic groups. As an
alternative, PA tends to be replaced by organic compounds containing
phosphonic acid groups, such as polyvinylphosphonic acid (PVPA).
Sinigersky et al. [121] [][][]prepared modified PBI-graft-PVPA mem­
brane with different length (Fig. S16 in supplementary information).
The proton conductivity of PBI membrane relied upon the concentration
of -PO3H2 groups and on RH to a great extent, nothing to do with the
length of grafted chain. The result showed that the proton conductivity
of the modified PBI-graft-PVPA membrane with highest -PO3H2 con­
centration was 35 mS cm− 1 (120 ◦ C, 100% RH) and 8 mS cm− 1 (120 ◦ C,
20% RH), respectively. Similarly, there are some reports about water
insoluble proton conductor used as the dopants in HT-PEMCs, like metal
sulfophenyl phosphates (MSPP, M = Zr, Fe and Ce). For example, Ferric
sulfophenyl phosphate (FeSPP) as a dopant for glass fiber (GF)/PBI
[122] and pre-oxidized acrylic fiber (POAF)/PBI [123], the structures of
these dopants are plotted in Fig. S17 (supplementary information). For
example, Sun et al. [122] prepared HT-PEMs containing OPBI, FeSPP
and GF using the hot-pressing method. Fiber was added to PBI to
improve the mechanical strength of the membrane, while FeSPP could
enhance the proton conductivity so that the trade-off problem of both
was addressed. Similarly, this tendency also can be observed for the
usage of POAF.
3. Aromatic polymer based HT-PEMs
The development of aromatic-based membranes with high perfor­
mance at anhydrous condition is still a challenge for significantly
improving the performance of HT-PEMFCs. Up to now, the well-
established polymeric electrolyte applied for HT-PEMFCs is PBI based
polymer. However, the PA leaching coupled with poor mechanical
properties at high temperature are major obstacles for widespread
application of PA-doped PBI membranes [124]. Therefore, some
Fig. 6. Typical structure of poly (arylene ethers).
9
Journal of Power Sources 533 (2022) 231386
properties, such as good thermal stability, mechanical stability and high
proton conductivity, need to be fulfilled for prospective development of
HT-PEMs [125]. A comprehensive understanding of developments in
non-PBIs is valuable in order to investigate novel electrolyte membranes
for HT-PEMFCs. This part mainly focuses on the properties of non-PBI
polymers with various functional groups as alternative HT-PEMs.
Grotthuss mechanism is considered to be the mainly proton transfer
mechanism at high temperature fuel cell system [126]. It is generally
supposed that most of non-PBI polymer are acid-base composites,
intrinsic protonic conductors except from this system, transporting
proton between acid groups and base groups [127]. The conductivity
mechanism of acid-base systems requires higher degree of proton
adsorption. Therefore, the alternative polymers generally should have
high affinity to strong acid molecules for preparation of HT-PEMs.
The most alternative HT-PEMs are probably poly(arylene ethers)
based membranes. As shown in Fig. 6, the rigid and bulky aromatic
groups in skeleton of poly (arylene ethers) can provide high glass tran­
sition temperature and outstanding mechanical stability over a broad
range of temperature. With very few exceptions, the poly(arylene
ethers) based polymers, including differently matched functionalities in
chain, have active sites with the advantage of proton adsorption due to
its processability, strong mechanical strength and high thermal stability
[125]. For example, the sulfonic acid group is proton exchange site and
is really important for proton conductivity. Therefore, sulfonate poly
(arylene ethers) polymers not only enhance the properties of poly
(arylene ethers), but also have high ionic exchange capacity (IEC) that
make it suit for application in PEMFCs.
To date, the application of poly (arylene ether)s and sulfonated ar­
omatic polymers have been discussed in several excellent reviews,
especially in the literature on low and medium temperature PEMFCs
[27,128–130]. Moreover, this type of polymer for HT-PEMFCs needs to
further investigate. Specifically, this part will review the application of
poly (arylene ethers) polymers at high temperature and low humidity
conditions.
Poly (ether ketone)s with different quantity of ketone and ether in
repeat units, a family of poly (arylene ethers), is commercially available
and has good properties similar to other engineering plastics. Unfortu­
nately, PA doped membranes could not easily disentangle the dilemma
between the proton conductivity, dimensional stability, and chemical
stability in this architecture. Zhao et al. introduced a series of poly
(arylene ether ketone)-g-quaternary 4-vinylbenzyl chloride comb-
shaped copolymers with quaternary ammonium groups on skeleton
structure (Fig. S18 in supplementary information) [131]. They
confirmed that the modification of PAEK by cross-linking enhanced the
property of membrane. It also observed that the amount of doping PA
was modified by the contents of quaternary ammonium groups (QA+) in
the repeat units. As a consequence, QA+ on PAEK skeleton had a good
capacity to fix PA molecules based on a hydrogen bonding interaction,
which efficiently improve the stability in mechanical strength. However,
E. Qu et al.
the membrane exhibited rather low proton conductivity of 31 mS cm− 1
at 120 ◦ C compared with pure PBI membrane.
Compared with PBI-based polymers, sulfonated poly(ether ether
ketone)s (SPEEK) are lower cost, high conductivities, and has promising
alternative to commercial HT-PEMs [132]. However, the chemical and
mechanical of SPEEK will be worse when the degree of sulfonation is
raised. In order to address the chemical stability and thermal stability
problem of SPEEK, many methods have been evolved. For example,
Yang et al. reported the SPEEK bearing imidazole groups application in
high temperature fuel cells [133]. The sulfonic acid groups in SPEEK can
react with imidazole groups which can as proton acceptors for PA
doping (Fig. S19a in supplementary information). The proton conduc­
tivity of membrane with low acid uptake level could reach 67 mS cm− 1
at 150 ◦ C, while the maximum peak power density of membrane was
209 mW cm− 2 at 150 ◦ C (Figs. S19b and c in supplementary informa­
tion). Recently, Raja K and co-workers reported the organic-inorganic
SPEEK/SPI/SrTiO3 composite membrane as HT-PEMs [134]. In order
to reinforce the properties of SPEEK, they added poly (amide imide)
(PAI) to the matrix. PAI provided hydrogen bonding with backbone of
SPEEK, while the hydrophobic of PAI could defeat the hydrophilic of
SPEEK. While the presence of SrTiO3 could enhance the water uptake as
well as proton conductivity which provided the interconnected and
continuous proton transport channels. The proton conductivity of
nano-composite membrane achieved 10.78 mS cm− 1 at 150 ◦ C.
Although there has been a hot topic about SPEEK, the chemical stability
of SPEEK remains an important issue to be addressed at high
temperatures.
Polysulfones show excellent thermal and mechanical stability, good
solubility in aprotic solvents, and easy to form film. Thus, the focus of
studies has been on the modification of main chain. Importantly, several
amphoteric N-heterocycles, such as pyrazole, imidazole, triazole, and
tetrazole, acting as both proton donors and acceptors, have been intro­
duced as proton carriers in PEMs. Lu et al. used atomic transfer radical
polymerization to prepare a type of poly(1-vinylimidazole)-grafted
polysulfone membrane (P-g-V), whose grafted imidazole group can act
as PA doping sites (Fig. S20 in supplementary information) [135]. The
imidazole heterocycles on backbone provide acid-base complexation
sites and enable the proton transportation of membranes. The prepared
PA-doped membranes had high proton conductivity of 127 mS cm− 1 and
peak power density of 559 mW cm− 2 at 160 ◦ C.
Generally, quaternary amine group and nitrogen heterocycles have
been utilized as the basic groups of acid-based composites. It is supposed
that the polymer with tailored basicity suitable for acid absorption and
proton transport. That is to say, these basic group on the polymeric chain
act as sites where interactions with PA could occur, thus increasing
quantity of protons for conductivity. There is prospective research to­
ward the development of aromatic polyether containing nitrogen het­
erocycles as proper candidates of HT-PEMs.
Poly(vinylpyrrolidone) (PVP), as a low-cost and widely used com­
mercial polymer, contains N-heterocycle and carbonyl groups, which
had high affinity to phosphoric acid through the hydrogen bond inter­
action [136]. However, PVP cannot be directly used as HT-PEMs due to
its extreme hydrophilicity and solubility in water. Thereby, PVP blended
with engineering thermoplastics, like polysulfone (PS), poly(ether­
ketone) (PEEK) or polyethersulfone (PES), have been developed as
alternative HT-PEMs due to the mechanical stability and simple fabri­
cation procedures. PES-PVP/PTFE membranes were prepared by
impregnating the porous PTFE membrane in PES-PVP solutions [137].
The SEM results proved the phase separation between PES and PVP. The
proton conductivity of the PES-PVP/PTFE composite membranes with
PA doping of 8 mol per mole of PVP repeating unit was reached 0.26 mS
cm− 2 at 180 ◦ C, and the peak power density was obtained 607 mA cm− 2.
After that, Lu et al. fabricated PVP-PVDF blend membranes in 2015
[138], in which hydrophilic PVP serves as proton accepter, while hy­
drophobic PVDF enhances mechanical strength. The anhydrous con­
ductivity of PA doped PVDF-PVP with 80 wt% PVP (PVDF-PVP80), was
10
Journal of Power Sources 533 (2022) 231386
0.093 S cm− 1 at 200 ◦ C. And the power density of PVDF-PVP80 reached
530 mW cm− 2.
In 2003, Kallitsis et al. [139]introduced the synthesis of flexible
membrane bearing polar pyridine and phosphinoxide in the repeating
unit. The presence of the pyridine and phosphinoxide group could
interact with PA, which would ensure the ability of consequently high
PA uptake and proton conductivity under the level of research at that
time. Lu et al. introduced a new type of polymer materials PAPs, which
were synthesized via a simple one-step method as shown in Fig. S21
(supplementary information) [140]. Moreover, the protonated piperi­
dine polymer exhibited excellent solubility and benefited for preparing
film. The resulted PPT/PA membrane showed proton conductivity of
96.0 mS cm− 1 at 180 ◦ C without humidification and tensile strength of
12 MPa. A single cell tests presented a power density of 1220.2 mW
cm− 2 at 180 ◦ C, which was the maximum power density of non-PBI
membrane. Moreover, the single cell test of PA doped PPT indicated
that this polymer could stability at a constant current density of 120 mA
cm− 2 and 150 ◦ C for 1600 h under H2/air condition.
In a work by Kim and his team, quaternary ammonium biphosphate
ion-pair-coordinated polyphenylene (QAPOH) as HT-PEMs could
conduct protons through stable ionic pair complexes and maintain a
high PA retention compared with acid-base coordinated PBI membrane
[141]. They pointed out that the electrostatic force of PA-QAPOH was
calculated to be eight times higher than the acid-base interaction be­
tween PA-PBI. The relatively strong basicity of quaternary ammonium
groups caused complete PA deprotonation, enabling a high PA content
in spite of water absorption or condensation. The PA retention suggests
that the primary benefit of the ion pair coordination over the acid-base
coordination is the enablement of wide operating temperature with the
increased water tolerance (Fig. S22b in supplementary information).
To date, many kinds of engineering polymer were used as main chain
of composite polymer for HT-PEM. Poly(phenylene oxide) (PPO) is one
of low-cost engineering polymer, which exhibits good thermal and
mechanical stability. However, the type of PPO normally does not
contribute to the conductivity directly. PPO can be used as PEM through
sulfonation, bromination and other modification of PPO. For example,
Zhou et al. reported a PA doped imidazolium PPO as HT-PEM [142], in
which the researcher grafted imidazole in sulfonated PPO realizing
proton adsorption and improving conductivities (Fig. S23a in supple­
mentary information). And the results indicated that the appropriate
quantity of imidazole group onto PPO endowed the conductivity of 67.9
mS cm− 1 and the peak power density of 280 mW cm− 2 in anhydrous
condition at 160 ◦ C. Lee et al. reported a cross-linked poly(2,
6-dimethyl-1,4-phenylene oxide) with triazole as proton acceptor [143].
This paper exhibited a new synthetic route for preparing cross-linked
membrane, which was synthesized on the side chains of PPO by in situ
casting and click reaction (Fig. S23b in supplementary information). In
this system, phenylene oxide applied as backbone of cross-linked
membrane, while triazole groups have interaction with PA for proton
transportation. The cell performance and mechanical stability could be
improved by the degree of cross-linking. Following this method, the
highest proton conductivity of PA-doped membrane was 64 mS cm− 1 at
180 ◦ C under anhydrous condition.
Polyphenylquinoxalines (PPQs) are promising polymers for fuel cell
applications because of outstanding thermal and mechanical properties
especially at elevated temperatures. Moreover, the researcher found
more doping active sites in the backbone of PPQs than commonly
polymer. Hsu had developed a novel crosslinked PPQs membranes as
HT-PEM (Fig. S24 in supplementary information) [144] the proton
conductivity of PA/PPQs was 130 mS cm− 1, while the peak power
density of membrane reached 148 mW cm− 2. Compared to other
acid-base membrane, the long-term durability test indicated steady
performance of PPQs.
Except aromatic poly(ethers) incorporating imidazole or pyridine
mentioned above, there is a small body of research on other nitrogen
containing heterocycles. For example, Henkensimeier et al. showed the
E. Qu et al.
fuel cell performance of PA doped tetrazole-containing poly(ether ether
nitrile) (PEEN) as HT-PEMs [145]. In this paper, the hydrogen bonds
between tetrazole and ether oxygen atoms were benefiting proton
hopping though poly(arylene ethers) backbone. Under the low PA con­
tents, the proton conductivity of resulting membrane could reach 25 mS
cm− 1 at 160 ◦ C, while the peak power density of 287 mW cm− 2 was
obtained.
High performance of PA doped electrolyte membrane requires a high
density of doped PA, while PA will acts as a plasticizer reducing the
mechanical properties [127]. At the same time, due to the crisis of doped
acid leaching, aromatic based polymers with protogenic group received
much attention in the field of HT-PEMFCs for several years [146]. It was
shown that phosphonic acid group has a prospective application as a
functional group in proton conducting electrolytes for HT-PEMs [125].
Most previous reports have showed that the phosphonic acid group have
higher proton carrier ability than other acid group especially under high
temperature and low humidification conditions. Therefore, the prepa­
ration of aromatic based polymers with phosphonic acid group have a
good prospective development. To date, various PA-functionalized
polyaromatics polymer have been synthesized, and the data indicate
that a high density of PA in skeleton is an important precondition for
reaching high proton conductivity [147]. Studies show that the proton
donor and acceptor properties combined with the high dielectric con­
stant of PA result in high degrees of self-dissociation [146]. Thereby, the
high degrees of self-dissociation and intense hydrogen-bond interaction
in PA-functionalized polyaromatics polymer endow high proton con­
ductivities. In addition, studies also have shown that synthesizing
phosphonic ionomers with high ion exchange capacity may improve
Fig. 7. (a) Synthesis of arylphosphonic acid polymer [151]; (b) synthesis of Poly(mPO) [152]; (c) conductivity for phosphonic acid polymer [151]; (d) conductivity
for Poly(mPO) [152].
11
Journal of Power Sources 533 (2022) 231386
performance of membrane. Insertion of acidic groups by covalent
bonding on the polymer backbone can reduce the drop in conductivity
during cell operation [148]. Then we summarize the various examples
on aromatic based polymers with proteogenic group as HT-PEMs.
Meng et al. described the preparation of phosphonic acid containing
poly(arylene ether)s as PEM [149]. And the result is as expected that the
conductivities of phosphonic acid containing polymers ranged from
10− 5 S cm− 1 and increased with the content of phosphonic acid.
Designing PA-functionalized polyaromatics polymer with high density
of acidic group and high IEC was proposed to achieve high conductiv­
ities for successful application of phosphorated polymers in high tem­
perature and/or low relative humidity. In recent work by Abouzari-Lotf,
a series of phosphorated copolyimide based on phosphorated diamine
monomer with high IEC was used as HT-PEMs under low humidity
conditions (Figs. S25a and b in supplementary information) [150].
Therefore, the interaction between imide groups and phosphonic acid or
water are probably responsible for stable conductivity (Fig. S25c in
supplementary information). At the same time, the thermogravimetric
analysis of phosphorated copolyimide confirmed the reliability of
application at high temperature.
In 2007, Timo Rager and co-workers prepared phosphonates poly(m-
phenylene) for fuel cell applications (Fig. 7a) [151]. However, the
proton conductivity of membrane was unsatisfactory (Fig. 7c), which
differed an order of magnitude from PBI-based membrane. Recently,
Reuben Hudson described the fabrication of poly(mPO)s containing
–SO3H, -PO3H2, –COOH on polymer skeleton for PEMFC applications
(Fig. 7b) [152]. More importantly, the authors compared the effect of
different acid moieties on proton conduction. They pointed that the
E. Qu et al. Journal of Power Sources 533 (2022) 231386

nature of the protogenic group and polymer backbone as underlying was modified by silane coupling agent, then sulfonated, and the proton
drivers of proton conductivity differences. Sulfonated polymers served transfer mechanism of membrane was enhanced by introducing sulfo­
as modest proton conductors under hydrated conditions, while phos­ nated group, eliminating or preventing the negative effect of agglom­
phonic acid functionalized polymers performed better at temperatures eration. This proved an effective method to prepare a new type of PBI
above 100 ◦ C under both hydrated and nominally dry conditions nano-composite membrane with high proton conductivity at low
(Fig. 7d). curing temperature based on rigid benzidine. Single cell test and acid
leaching test showed that the maximum power density of the composite
4. Composite membranes for HT-PEMs membrane was 621 mW cm− 2, which was approximately 30%
improvement, compared to pure PBI membrane (471 mW cm− 2).
Composite modification is a common method for polymer membrane Meanwhile, the retention of PA was also increased (Fig. S27b in sup­
modification. It is expected that each part of the composite can give full plementary information).
play to self-advantages and make up for the shortcomings of other Nawn et al. [166] prepared a series of composite membranes from
components. In order to effectively solve poor mechanical performance nano-ZrO2 and poly[2,2′ -(m-phenylene)-5,5′ -bibenzimidazole] (PBI4N).
prompted by high doping level and the loss of PA at extreme tempera­ ZrO2 broke the strong hydrogen bond between imidazole groups in
ture, adding inorganic nano-filler to PA doped PBI membrane is a m-PBI through the interaction between ZrO2 and Lewis basic nitrogen
feasible strategy. Generally speaking, inorganic fillers can be divided atom of PBI4N, and played a plasticizing role in the composite mem­
into five categories: (I) inert hydroscopic oxides, such as SiO2, zeolites, brane. When the doping amount of ZrO2 was 0.231 (the molar ratio of
montmorillonites and TiO2, etc.; (II) proton conductor, such as hetero­ ZrO2 to PBI4N repeat unit), the proton conductivity of [PBI4N
polyacids (SiWA, PWA, PMoA), Cesium salts of heteropolyacids (HPAs), (ZrO2)0.231] (H3PO4)13 composite reached 0.104 S cm− 1 at 185 ◦ C,
POSS (polyhedral oligomeric silsesquioxane) and zirconium oxide or making this type of membranes promising for HT-PEMFCs. Aili et al.
salts, especially zirconium hydrogen phosphate (ZrP), which can in­ [167] prepared the composite membrane of PBI and sulfonated poly­
crease acid sites and provide additional paths for proton transport; (III) hedral oligosilsesquioxane (POSS), and the structure of PBI and S-POSS
clay; (IV) carbon-based materials; (V) metal organic frameworks is shown in Fig. S28 (supplementary information). The introduction of
(MOFs). A selection of PBI-based PEMs with common filler are tabulated S-POSS made PA-doped PBI composite membranes deliver higher proton
in Table 3. conductivity than PA-doped pure PBI membranes. The conductivity
As we know, hydrophilic inorganic fillers are not acidic and their upgrades were also verified using in situ fuel cell tests at 160 ◦ C through
aggregation occurs at high particle concentration, so their addition may electrochemical impedance spectroscopy and polarization data.
actually bring about the decrease of proton conductivity [153]. There­ Furthermore, the conductivity of the PBI membrane containing 10%
fore, present research has paid attention to functionalized fillers so as to S-POSS was 0.11 S cm− 1 and 0.19 S cm− 1 under anhydrous and full
enhance the membrane durability without sacrificing proton conduc­ humidity at 180 ◦ C, respectively, and the maximum power density was
tivity. Suryani et al. [154] prepared PBI-functionalized silica 440 mW cm− 2 for H2/O2 fuel cell at 160 ◦ C, indicating the feasibility of
nano-particles to modify PBI nano-composite membranes the novel electrolyte materials.
(PBI/SNP-PBI). The SNP-PBI was synthesized according to the Heteropolyacids, like phosphotungstic acid (PWA), can ameliorate
ozone-mediated process from the anterior report [155] by utilizing the the mechanical properties and proton conductivity of PBI, but their
precursors of N-(p-carboxyphenyl)maleimide functionalized SNPs water-solubility may have a certain adverse effect on the durability of
(SNP-Pcpm) to form chemical bond between PBI and the SNP surface such membrane. Wang et al. [168] fixed PWA on silica to prepare
(Fig. S26a in supplementary information). The proton conductivity of SiO2-riveted PWA (T-PWA-SiO2) by the sol-gel method and microwave
PBI/SNP-PBI nano-composite membrane with 10 wt% of SNP-PBI heat treatment of PWA and tetraethyl chlorosilane and used it as an
(SNP-PBI-10) was 25% higher than that of the pristine PBI at 160 ◦ C additive of ABPBI through the hydrogen bonding interactions between
(Fig. S26b in supplementary information). Moreover, its maximum PWA and C– – N in ABPBI (Fig. S29 in supplementary information).
power density reached 650 mW cm− 2 in a single cell test, which was far Compared to the sample without thermal treatment (PWA-SiO2), the
better than that of the pristine PBI membrane (530 mW cm− 2) (Fig. S26c PWA in T-PWA-SiO2 delivered better fastness from the
in supplementary information), demonstrating the enhancement of the dissolving-detaching experiment result. Additionally, owning to higher
acid retention capacity and proton conductivity. PWA contents could increase the concentration of mobile protons, the
Similarly, Lee et al. [165] prepared chemically-functionalized tita­ proton conductivity and durability of the ABPBI/(T-PWA-SiO2) com­
nium nano-particle/polybenzimidazole (PBI-sTP) high temperature posite membranes were better than those of ABPBI/(PWA-SiO2) com­
anhydrous PEMs (Fig. S27a in supplementary information), where TiO2 posite membranes. At 180 ◦ C and 100% RT, the conductivity of
ABPBI/(T-PWA-SiO2) (46 wt%) composite membrane was about 0.055
S cm− 1.
Table 3 CsHSO4(Cesium hydrogen sulfate) is an inorganic solid proton
Examples of PA doped PBI-based PEMs with common filler. conductor. Cesium and other sulfate oxonium show phase transition to
Category Organic Inorganic phase/ Proton Ref fast proton phase at 140 ◦ C. Above this temperature, the proton con­
phase Loading (%) Conductivity ductivity rises rapidly to 10− 3-10− 2 S cm− 1. Cesium salt and its sulfate
(mS⋅cm− 1) (T/◦ C, are usually formed as proton conductors in the form of pure pellet or
RT/%)
composite with polymer materials, but the superior proton conductivity
Hydroscopic PBI SiO2/5 103 (180, 0) [156] of the membrane cannot be measured above the phase transition tem­
oxides TiO2/5 44 (180, 0) [157]
perature. Haile et al. [169] reported a solid acid battery, using CsH2PO4
Proton PBI ZrP/15 96 (200, 5) [158]
conductor PWA/30 58 (200, 5) [158] as an electrolyte, which could reach 134 mW cm− 2 of power density. The
SiWA/40 177 (150, 0) [159] solid acid exhibited fast proton phase transition at 231 ◦ C, which was
SrCeO3/8 105 (180, 0) [160] expected to be used as a high temperature mixed acid doped poly­
ABPBI OctaAmmonium >100 (160, 0) [161] benzimidazole fuel cell membrane. More recent studies mixed CsHSO4
POSS/4
clay PBI organically modified – [162]
with nanometer-scale microporous zeolite to improve conductivity
Na+-bentonite [170]. However, these published articles didn’t investigate the perfor­
(OMBP) mance of single fuel cell at high operating temperatures. In terms of
carbon-based PBI GO/2 170 (180, 0) [163] polymer membranes, these materials can provide a promising candidate,
materials PBI CNT/1 74 (180, 0) [164]
however, the challenges of mechanical unsteadiness, water solubility

12
E. Qu et al.
and compatibility with other cell parts need to be solved.
Carbon-based proton conductors, including graphene, graphene
oxide (GO), carbon nano-tubes (CNTs), fullerenes and their derivatives,
have been developed and widely studied due to their cheap and non-
toxic nature, which can be used as one of the inorganic fillers for pre­
paring PBI composite membranes. Carbon nano-tubes (CNTs) have been
utilized as reinforcement in polymer membranes, primarily to enhance
mechanical and electrical performance. The preparation of uniformly
dispersed CNT/polymer composite membranes relies on good interfacial
binding among the components [171]. However, the preparation of
composites between PBI and CNTs must be discreetly evaluated due to
the electronic conductivity, which may induce short circuits in the cell.
Therefore, the nano-composite without non-destruction to CNTs may be
a fascinating aim in terms of preparing the conductive composites [172].
Moreno et al. [173] prepared PBI non-functionalized multiwalled car­
bon nano-tube (MWCNT) composite membranes and investigated the
role of MWCNT in composite. The conductivity of PA doped PBI-CNT
membrane (PBICNTPA) (74 mS cm− 1) was higher than that of PA
doped PBI membrane (PBIPA) (63 mS cm− 1) at 180 ◦ C&0% RH due to
better PA retention after adding CNT. Moreover, the maximum power
density and open circuit voltage the PBICNTPA membrane (174.5 mW
cm− 2, 0.96 V) was higher than that of PBIPA membrane (153 mW cm− 2,
0.8 V) at 180 ◦ C in a single H2/O2 fuel cell. The results indicate that
PBI-CNT composites membranes are a suitable alternative material for
HT-PEMFCs.
Recently, except for CNTs, graphene oxide (GO) prepared by the
exfoliation of graphite oxide nano-plates has also attracted the attention
of researchers because of its remarkable mechanical properties, wide
specific surface area and low cost. PA functionalized fillers can furnish
superior dispersion and increase the compatibility of polymer fillers,
which has a direct influence on dimensional stability and mechanical
strength of the membranes.
For example, Abouzari-Lotf et al. prepared highly durable 2,6-pyri­
dine functionalized PBI composite membranes (Py-PBI/PGO) by
employing highly dispersible phosphorated GO (PGO) (Fig. S30a in
supplementary information) [174]. The conductivity of Py-PBI/PGO/PA
composite membrane with 1.5% PGO incorporation (76.4 mS cm− 1) was
higher than that of PA doped Py-PBI membrane (19.6 mS cm− 1) under
similar conditions at 140 ◦ C (Fig. S30b in supplementary information),
because the inherent strong hydrogen bonding from imide groups of
Py-PBI and localized phosphonic acid contribute to the formation of an
efficient proton transport network. Moreover, compared with the
membranes without the phosphorated filler, the maximum power den­
sity of Py-PBI/1.5PGO/PA composite membrane reached 359 mW cm− 2
at 120 ◦ C &0% RH that was above 75% increasements, which may be
due to the excellent stability of PA in the membrane structure containing
PGO. The results indicate that the strategy of preparing this kind of
composite membrane provide the way for high conductivity and durable
PEMs and has a potential for application in HT-PEMFCs.
Clay-reinforced polymer composites are famous for their advantages
of excellent thermal and chemical stability, mechanical strength and
modulus, dimensional, flame retardancy and barrier properties [175].
PBI polymer electrolytes containing clay are expected to enhance the
durability and performance of fuel cells. Two kinds of organically
modified nano-clays with ammonium and pyridinium salts, including
clay L and clay N, were synthesized and used to prepare PBI composite
membrane [176]. Among PBI/clay N composite membrane, the highest
proton conductivity was 120 mS cm− 1 at 150 ◦ C and 12% RH (15 wt%
clay N, ADL 12.0), which was much higher than the unfilled pure PBI
membrane (Fig. S31a in supplementary information). Besides, for
PBI/clay L composite membrane with 5 wt% clay L, when ADL was 8.2,
the current density achieved 210 mA cm− 2 at a cell voltage of 0.6 V
(Fig. S31b in supplementary information).
In the last few years, MOFs used as fillers has aroused wide attention
of researchers. Zeolitic imidazolate frameworks (ZIFs) with excellent
chemical stability, thermal stability, and high porosity is a special
13
Journal of Power Sources 533 (2022) 231386
subgroup among MOFs [177]. Lately, Escorihuela et al. [178] synthe­
sized a co-based ZIF-67, a Zn-based ZIF-8, a compound of the two
(ZIF-mix), and then they were acted as filler to prepare PA doped
composite membranes of PBI with 5 wt% fillers, including PBI@ZIF-67,
PBI@ZIF-8 and ZIF-mix(Fig. S32 in supplementary information). The
testing results for proton conductivity showed that the value of PA
doped PBI@ZIF-67 and PBI@ZIF-mix membrane at 200 ◦ C were 41 mS
cm− 1, 91 mS cm− 1, respectively, indicating the synergistic reaction of
the two MOFs, which could lead to more continuous hydration channels.
Additionally, Uio-66, a subclass of MOFs, has also been used to develop
efficient MOF based proton conductors [179,180]. Mukhopadhyay et al.
[181] prepared PBI composite membrane with post synthetically
modified (PSM) UiO-66-NH2-MOFs with 10 wt% fillers (Fig. S33 in
supplementary information). After using PSM 1 and PSM 2 MOFs
nano-filler, the resultant OPBI composite membrane delivered excellent
proton conduction due to extensive interfacial H-bonding. The con­
ductivity of OPBI/PSM 1 and OPBI/PSM 2 composite membrane was
290 mS cm− 1, 308 mS cm− 1 at 160 ◦ C& 0 RH, respectively, which are
higher than most MOF based polymer supporting membranes. This
paper can open a path way for obtaining efficient proton conducting
membranes used in HT-PEMFCs.
Except for adding inorganic nano-filler to PA doped PBI membrane,
organic fillers also become attractive due to its low price, low density,
renewable and other characteristics. Schecheter and Savinell reported
[182] that PA doped PBI electrolyte containing imidazole (IM) and
1-mentyl imidazole (Me-Im). The influence of IM and Me-Im on the
conductivity of liquid H3PO4 99% (wt) solutions and on PA doped PBI
membranes was investigated under wide temperature range and
different humidification levels. The proton conductivity of PA doped PBI
decreased after adding IM and Me-Im, which was assigned to the
decrease of the number of proton charge carrier (PCC) as a direct result
of the acid and basic molecule reactions. The results suggest that it can’t
enhance the conductivity of PBI/H3PO4 membrane, and the “free” un­
bounded acid and water molecules are the dominating contributors
instead of conduction through the addition of salt or PBI+H2PO4− chain.
A main defect of PA doped PBI membrane is the leakage of doped acid.
In order to reduce acid leakage, some hydrophobic phosphoric acid
derivatives are used as dopants to dope PBI and ABPBI. Jiang et al. [183]
prepared water-free tridecylphosphate (TP)-PBI membrane with ther­
mal stability up to 145 ◦ C(Fig. S34 in supplementary information).
However, the proton conductivity of these anhydrous membranes was
too low to be used as PEMs (10− 4 S cm− 1 at 140 ◦ C; 5 × 10− 6 S cm− 1 at
room temperature). But most water-free sub-conducting membranes
have been studied in recent years on account of inorganic or partially
inorganic materials. In this paper, the composite was fully based on
organic components, indicating that this strategy can provide a new idea
for the subsequent research on PBI composite membranes.
Additionally, in recent years, for non-PBI based composite materials
as HT-PEMs have been investigated. He et al. synthesized carbon dots
(CDs) possessing different hydrophilicity into PVP-PES blended poly­
mers as organic-inorganic composite PEMs [184]. The molecular level
sized CDs could cause the changes in acid doping level and benefit
proton conduction of Poly(vinylpyrrolidone) and polyethersulfone
blend membrane. The peak power density of the blend membrane is
165.5 mW cm− 2 at 150 ◦ C which is observably higher than that of the
pristine blend membrane-based cell.
Lu et al. introduced graphitic carbon nitride (CN) nano-sheets into
PES-PVP matrix to prepare blend membrane through simple blending
process [185]. Graphite-like carbon nitride (CN) was incorporated into
PES-PVP blends to improve the properties of HT-PEMs. The introduction
of CN nano-sheets could increase PA doping level due to the interaction
between CN and acid molecules, and the proton conductivities of the
composite membranes increased from 120 to 180 ◦ C. Particularly, the
peak power density of single cell with P/CN-0.5/PA reached 634 mW
cm− 2 at 180 ◦ C.
Moreover, nano-fibers reinforced composite polymers have been
E. Qu et al.
used to prepare HT-PEMs. Chen et al. used Kevlar nano-fibers supporting
the composite membrane for HT-PEMFCSs [186]. In this research, the
multilayered membranes were prepared with spin coating method,
depositing Kevlar nano-fibers, CdTe nano-crystals and PA molecules
alternately (Fig. S35 in supplementary information). The composite
membrane exhibited satisfactory proton conductivity stability and me­
chanical property, while the proton conductivity reached 235 mS cm− 1
at 160 ◦ C. However, the aramid structure of Kevlar is prone to hydro­
lysis, which cannot stabilize in PA, especially at high temperature.
Therefore, the chemical stability of aramid polymer is an obstacle under
acidic conditions, which need attention for further reach.
Different from the intrinsic protonic conductors described above,
diversity of solid acid electrolytes has been investigated recently, for
example, ammonium polyphosphate, pyrophosphate, cesium phosphate
and other phosphate-based composites material [147]. Solid acids are
known for inherently conductive property and stability combining
monovalent metal cations tetrahedral oxyanions. Paschos made an
overview of the solid acid knowledge, in relation to the mechanisms
transport and the properties of solid acids. The proton transport mech­
anism lies in the electrolyte structure still the open questions for solid
acids. In general, the conductive fundamental of solid acid are the phase
transitions and phosphate group disorder which can form hydrogen
bonds network [187]. During the various solid acids, cesium dihydrogen
phosphate (CsH2PO4) and CsHSO4 are relatively well-studied solid acids
at high temperature under anhydrous condition. For example, Li et al.
reported a composite electrolyte membrane combing CsH2PO4 and
SPEEK with phosphosilicate [188]. This simple method endows the
CsH2PO4 based membrane with comprehensive performance befitting
used at high temperature. The proton conductivity could keep above
10− 3 S cm− 1 between 140 ◦ C and 230 ◦ C under anhydrous condition. Cai
constructed a LaF3–CsH5(PO4)2 composite electrolyte, which could form
dense hydrogen bonds between –OH in CPD and –F in LaF3 [189]. In this
paper, the role of LaF3 was elevate the thermomechanical property of
CPD. Meanwhile, the synergistic effect of hydrogen bonds and the
intrinsic conductivity of CsH5(PO4)2 endowed the conductivity of
composite reaching 30.1 mS cm− 1 at 150 ◦ C under dehydrated
condition.
In order to keep the balance between proton conductivity and me­
chanical properties, the addition of the filler into matrix is an effective
method. For example, Elumalai et al. reported phosphonation of
PPSEBS/PSBA-15 for HT-PEM recently, which was synthesized by
incorporating phosphonated SBA-15 into the phosphonated poly
(styrene-ethylene/butylene-styrene) (Fig. S36 in supplementary infor­
mation) [190]. The phosphonic acid group in the PABA-15 backbone
could contribute to proton conduction, meanwhile as an immobilized
proton solvent in the composite membrane with mechanical and elec­
trochemical stability.
5. Fluorinated polymer for HT-PEMs
In the past few decades, the development of proton conducting ma­
terials has produced a variety of perfluorinated polymer electrolyte
membranes due to the high electronegativity and low polarizability of
fluorine, such as Nafion produced by DuPont, Which show excellent
physical and chemical stability. However, there are some disadvantages
inhibiting its application. For example, the proton conductivity of this
kind of polymer membrane will decrease dramatically at elevated
operating temperature (>100 ◦ C) or low humidity owning to the inde­
pendent on liquid water serving as the proton conductor. Nevertheless,
it is a good strategy to apply it to acid doped HT-PEMs. For instance, the
solubility of PBI in organic solvent could be improved by introducing
organofluoride groups [191]. Chuang et al. [192] synthesized a new
fluorine-containing PBI for HT-PEMFCs through molecular modifica­
tion. Compared to PA doped PBI membranes, the conductivity of Nafion
117 membrane declined abruptly after 80 ◦ C owning to dehydration. But
for PBI membranes, its conductivity increases with increasing both
14
Journal of Power Sources 533 (2022) 231386
temperature and ADL content. The conductivity of PBI-3.0H3PO4 could
reach 1.7 × 10− 4 S cm− 1 at 160 ◦ C, which is much higher than that of
Nafion 117 membrane (Fig. S37 in supplementary information). Li et al.
[193] found that the chemical stability along with solubility of PBI can
be improved significantly by introducing the electron-deficient bridging
groups –C(CF3)2- into polymer chain. Furthermore, the ionically
cross-linking in the form of acid-base interaction was realized by
blending the modified PBI with partially fluorinated sulfonated aromatic
polyether, which was found to further improve the polymer stability and
assist membrane integrity. Similarly, Pu et al. [194] introduced
fluorine-containing groups to the PBI backbone, the corresponding
membrane had higher doping level and proton conductivity. Compared
to non-fluorinated analogue, higher proton conductivity was shown
with higher fluorine content, which could be assigned to the large
electronegativity of fluorine, making the protons near the –NH group
more acidic.
Ghassemi et al. [195] reported the synthesis of phosphorated poly
(arylene ether)s (Fig. S38 in supplementary information) and the
resulted phosphorated polymer could make tough and transparent
membrane. The presence of highly concentrated acid groups next to
perfluorinated biphenyl rings could increase acidity and aggregation of
phosphonic acids which may provide a better condition for higher
proton conductivity. During the test, this type of membrane did not
require PA doping. Finally, the proton conductivity of the phosphonate
membranes reached 150 mS cm− 1 at fully hydrates condition.
Jalili et al. assembled a HT-PEM combine mobile protons source with
proton-hopping sites by acid-base reaction between non­
afluorobutanesulfonic acid (NFBSA) or p-toluenesulfonic acid (p-TSA)
with nitrilotri(methylenephosphonic acid) (NTMPA) (Fig. S39 in sup­
plementary information) [196]. The NTMPA behaved as a Brønsted base
which would capture proton from p-TSA or NFBSA, thereby the trans­
parent and tough proton-conductivity membrane were obtained. More
importantly, the activity of POH in the NTMPA moiety could enable
proton transport. Fortunately, the NFBSA/NTMPA and p-TSA/NTMPA
ionic composites had a denser hydrogen-boning for efficient proton
transport. More importantly, the proton migration mechanism of solid
protic ionic was strongly based on the hydrogen bonding network.
Finally, the conductivity of those polymer solid ionic could be in excess
of 10− 2 Ω− 1 cm− 1 at 190 ◦ C under anhydrous condition.
With the continuous deepening of the research, Wu et al. [197]
constructed perfluoroalkyl-functionalized two-dimensional COFs with
superhydrophobicity for anhydrous proton conduction via a bottom-up
self-assembly method (Fig. 8). Compared to the fluorine-free COFs, the
fluorinated COFs have superior structural stability against strong acids
due to its improved hydrophobicity (water contact angle of 144◦ ), and it
can be stable in concentrated PA (85%), concentrated nitric acid (65%)
and concentrated hydrochloric acid (38%). The results suggested that
the proton conductivity of PA doped fluorinated COFs (COF–F6–H) was
4.2 × 10− 2 S cm− 1 at 140 ◦ C&0% RH, and it was 10000 times higher
than that of fluorine-free COFs. This is currently one of the highest ex­
amples for anhydrous proton transport performance of the organic
porous materials. This paper provides a successful example of functional
modification for COFs in order to realize its directional functionalization
via pore structure design, and it open the way for predesign and func­
tionalization of the pore surface to achieve the target performance of
COFs and manifests enormous potential of COFs nano-channels as a
rapid ion transport platform.
Kim et al. [198] reported HT-PEMFCs based on quaternary
ammonium-biphosphate ion pairs which could not undergo anhydride
formation below 240 ◦ C. They point out that the formation of phos­
phonic anhydride of phosphorated polymers was the primary reason for
low proton conductivity and poor long-term durability over high tem­
perature range. In order to break through the operating temperature of
HT-PEMFCs, poly (2,3,5,6-tetrafluorostyrene-4-phosphonic acid)
(PWN70) was prepared and compared with poly (vinylphosphonic acid)
(PVPA) (Fig. S40a in supplementary information). In contrast to PVPA,
E. Qu et al.
Fig. 8. Synthesis of (a) COF–F6 and (b) COF–F6–H by doping H3PO4 doped COF–F6 (COF–F6–H); (c) Nyquist plot for COF–F6–H at different temperatures; (d)
Conductivity of COF–F6–H with a different amount of H3PO4 [197].
the proton conductivity of PWN70 remained stable over 100 h, which
had mitigated anhydride formation primarily owing to the strong elec­
tron withdrawing fluorophenyl group of PWN70 (Fig. S40b in supple­
mentary information). However, the PVPA, which has
methylphosphonic acid group, inclined to anhydride formation owing to
the intermolecular and intramolecular condensation. As shown in
Fig. S40c (supplementary information), they combined PWN70 with an
ion-pair coordinated membrane in a MEA and then evaluated the
long-term durability at a constant high current density, indicating the
structural stability of PWN70. In future work, fluorinated polymer will
be a trend to improve PA stability of HT-PEMs.
15
Journal of Power Sources 533 (2022) 231386
6. Conclusive remarks
HT-PEM is the core component of HT-PEMFCs, which can conduct
protons and isolate electrons between electrodes. Overall, it is necessary
to develop HT-PEM with superior performance at high temperature and
under anhydrous condition. A comprehensive understanding of the
relationship between physical properties and electrochemical perfor­
mance of HT-PEMs is very important to develop high performance HT-
PEMFCs. There are many kinds of membrane for HT-PEMFCs, and the
associated performance of membrane recently reported is summarized
in Table 4. Among different types of membranes explored, PA-doped PBI
membrane shows comparative performances, which meet most objec­
tives of DOE (except durability) for HT-PEMs. The modification of PBI
based HT-PEMs should focus on how to improve the durability. The
E. Qu et al. Journal of Power Sources 533 (2022) 231386

Table 4
Summary of some representative membranes in HT-PEMFCs.
Membrane Main chain structure Fabrication and Test Conditions Conductivity Fuel cell performance Ref.
type (mS⋅cm− 1)
T/ RH/ Gas Electrocatalyst mixture Voltage Peak power
◦
C % (V) density (mW/
cm2)

m-PBI 160 – – – 160 – – [199]

p-PBI 160 240 [200]

AB-PBI 110 60 [201]

F6-PBI 160 – 90 [202]

P0.5-b-O0.5-PBI 160 0 80 mL min− 1 H2/ Anode& Cathode 100(180 ◦ C) ~0.91 360 [87]
160 mL min− 1 air catalyst: Pt (Pt/C)
PBI–5.3%BeIm 160 0 100 mL min− 1 H2/ carbon-supported 150 ~0.95 351 [106]
200 mL min− 1 air catalyst (57 wt% Pt/C)

PBI-NH2-EPA- 170 0 – – 62 – – [107]

15

PBI-2% TiO2 – 150 10 134 mL min− 1 H2/ 40% Pt on carbon black 130 ~0.83 800 [203]
76 mL min− 1 O2
SPEEK/PBI 170 100 – – 198.5 – – [204]
(20 wt%)

PBI-20%TMBP 150 0 – 51 [116]

QOPBI-15 160 0 H2/air 49 0.8–0.85 260 [205]

PBI-sTP2 150 0 100 sccm H2 and Pt/C and PFTE sprayed 96 ~0.95 621 [165]
O2 onto GDL

PBI-5% ZrP – 180 0 – – 200 – – [206]

PBI-30% – 150 0 H2/O2:300–400 50 wt% Pt/C and PTFE 120 >0.95 600 [207]
CsPOMo mL min− 1 solution (60 wt%
Aldrich)
1
Py-PBI-1.5% – 140 0 600 mL min− H2/ Pt–C (40 wt% Pt) 76.4 0.88–0.94 360(120 ◦ C) [174]
1
PGO 600 mL min− air
PBICNTPA – 180 0 H2/O2 20 wt% Pt on carbon 74 0.96 174.5 [173]
black
− 1
PBI-15% 150 12 100 mL min H2/ 40 wt% Pt supported on 120 0.91–0.96 220 [176]
1
laponite 200 mL min− air carbon black
clay-N
PBI-5% ZIF- – 200 0 – – 92 [178]
8+ZIF-67
PBI-graft- 120 20 8 [121]
PVPA

PA/Kevlar- 160 – – – 235 – – [186]

CdTe-PA

trade-off between the proton conductivity and mechanical property, and
the leakage of PA during the fuel cell operation are the main faced
problems for the development of PBI based HT-PEMs. In addition to PBI-
based membrane, non-PBI membrane with superior performance is a
prospective approach to alleviate PA leaching problems, poor mechan­
ical and chemical stabilities for HT-PEMFCs. Up to now, recent re­
searches on PA doped poly (arylene ethers), polymer skeleton with
grafting intrinsic proton conducting groups, fluorinated polymer and
composites materials have been widely developed for HT-PEMFCs. Some
new proton conducting models were proposed for non-PBI HT-PEMs,
whose proton conductivity are still need to improve for high fuel cell
performances.
To focus on the challenges of HT-PEMs, the modification and future
research directions of HT-PEMs are believed to cover: (1) intrinsic
proton conducting groups should be introduced into the backbone of the
polymer, which can serve as proton sources to decrease the doping level
of free PA in membrane, thus the relationship between the proton con­
ductivity and mechanical stability can be balanced; (2) stronger basicity

16
E. Qu et al.
polymer with strong PA interactions are promising candidates to replace
PBI polymer because of their excellent acid retention ability and proton
conduction at high temperature and under anhydrous condition. To
accelerate the development of HT-PEMFCs, new type of HT-PEM with
excellent practical performance is crucial.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgment
This work was supported by the National Key Research and Devel­
opment Program (2018YFA0702002), the National Key Research and
Development Program (Japan-China Joint Research Program)
(2017YFE0197900), National Natural Science Foundation of China
(22179149, 22075329, 51573215, and 21978332), Guangdong Basic
and Applied Basic Research Foundation (Grant No. 2021A0505030022,
2019A1515010803, 2020A1515011445); Guangzhou Scientific and
Technological Planning Project (Grant No. 201904010271); the
Fundamental Research Funds for the Central Universities (Grant
No.19lgpy07, 20lgpy11).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jpowsour.2022.231386.
References
[1] Y. Gao, J. Pan, Z. Yang, F. Gao, G. Ji, Optimization based accurate scheduling for
generation and reserve of power system, Sci. China Technol. Sci. 55 (2012)
223–232.
[2] P. De Luna, C. Hahn, D. Higgins, S.A. Jaffer, T.F. Jaramillo, E.H. Sargent, What
would it take for renewably powered electrosynthesis to displace petrochemical
processes, Science 364 (2019) 350–358.
[3] J. Luis, L.M. Sidek, M. Desa, P. Julien, Sustainability of hydropower as source of
renewable and clean energy, IOP Conf. Ser. Earth Environ. Sci. 16 (2013),
012050.
[4] D. Shindell, C.J. Smith, Climate and air-quality benefits of a realistic phase-out of
fossil fuels, Nature 573 (2019) 408–411.
[5] S.d.I.R. du Can, L. Price, Sectoral trends in global energy use and greenhouse gas
emissions, Energy Pol. 36 (2008) 1386–1403.
[6] R. Paul, L. Zhu, H. Chen, J. Qu, L. Dai, Recent advances in carbon-based metal-
free electrocatalysts, Adv. Mater. 31 (2019) 1806403–1806426.
[7] S.E. Hosseini, M.A. Wahid, Hydrogen production from renewable and sustainable
energy resources: promising green energy carrier for clean development, Renew.
Sustain. Energy Rev. 57 (2016) 850–866.
[8] Q. Zhao, Z. Yan, C. Chen, J. Chen, Spinels: controlled preparation, oxygen
reduction/evolution reaction application, and beyond, Chem. Rev. 117 (2017)
10121–10211.
[9] S. Chu, Y. Cui, N. Liu, The path towards sustainable energy, Nat. Mater. 16 (2017)
16–22.
[10] S.r. Dresp, F. Dionigi, M. Klingenhof, P. Strasser, Direct electrolytic splitting of
seawater: opportunities and challenges, ACS Energy Lett. 4 (2019) 933–942.
[11] Z.W. Seh, J. Kibsgaard, C.F. Dickens, I.B. Chorkendorff, J.K. Nørskov, T.
F. Jaramillo, Combining theory and experiment in electrocatalysis: insights into
materials design, Science 355 (2017) 146–179.
[12] S. Anantharaj, S.R. Ede, K. Sakthikumar, K. Karthick, S. Mishra, S. Kundu, Recent
trends and perspectives in electrochemical water splitting with an emphasis on
sulfide, selenide, and phosphide catalysts of Fe, Co, and Ni: a review, ACS Catal. 6
(2016) 8069–8097.
[13] S.W. Chuang, H. Steve Lien-Chung, L. Yen-Hsin, Synthesis and properties of
fluorine-containing polybenzimidazole/silica nanocomposite membranes for
proton exchange membrane fuel cells, J. Membr. Sci. 305 (2007) 353–363.
[14] M. Mamlouk, K. Scott, A boron phosphate-phosphoric acid composite membrane
for medium temperature proton exchange membrane fuel cells, J. Power Sources
286 (2015) 290–298.
[15] H. Zarrin, G. Jiang, Y.Y. Lam, M. Fowler, Z. Chen, High performance porous
polybenzimidazole membrane for alkaline fuel cells, Int. J. Hydrogen Energy 39
(2014) 18405–18415.
[16] C. Yang, P. Costamagna, S. Srinivasan, J. Benziger, A.B. Bocarsly, Approaches and
technical challenges to high temperature operation of proton exchange
membrane fuel cells, J. Power Sources 103 (2001) 1–9.
17
Journal of Power Sources 533 (2022) 231386
[17] S. Bose, K. Tapas, N. Thi Xuan Hien, K. Nam Hoon, L. Kin-tak, L. Joong Hee,
Polymer membranes for high temperature proton exchange membrane fuel cell:
recent advances and challenges, Prog. Polym. Sci. 36 (2011) 813–843.
[18] B. Smitha, S. Sridhar, A.A. Khan, Solid polymer electrolyte membranes for fuel
cell applications-a review, J. Membr. Sci. 259 (2005) 10–26.
[19] Y.-J. Wang, J. Qiao, R. Baker, J. Zhang, Alkaline polymer electrolyte membranes
for fuel cell applications, Chem. Soc. Rev. 42 (2013) 5768–5787.
[20] T. Omasta, L. Wang, X. Peng, C. Lewis, J. Varcoe, W.E. Mustain, Importance of
balancing membrane and electrode water in anion exchange membrane fuel cells,
J. Power Sources 375 (2018) 205–213.
[21] D. Herranz, P. Ocón, Benzimidazole as solid electrolyte material for fuel cells, in:
Chemistry and Applications of Benzimidazole and its Derivatives, IntechOpen,
2019.
[22] M. Tanaka, K. Fukasawa, E. Nishino, S. Yamaguchi, K. Yamada, H. Tanaka,
B. Bae, K. Miyatake, M. Watanabe, Anion conductive block poly (arylene ether) s:
synthesis, properties, and application in alkaline fuel cells, J. Am. Chem. Soc. 133
(2011) 10646–10654.
[23] D. Klaus Kreuer, Ion conducting membranes for fuel cells and other
electrochemical devices, Chem. Mater. 26 (2014) 361–380.
[24] J.X. Leong, W.R.W. Daud, M. Ghasemi, K.B. Liew, M. Ismail, Ion exchange
membranes as separators in microbial fuel cells for bioenergy conversion: a
comprehensive review, Renew. Sustain. Energy Rev. 28 (2013) 575–587.
[25] V. Vijayakumar, S.Y. Nam, Recent advancements in applications of alkaline anion
exchange membranes for polymer electrolyte fuel cells, J. Ind. Eng. Chem. 70
(2019) 70–86.
[26] F.A. De Bruijn, V. Dam, G. Janssen, Review: durability and degradation issues of
PEM fuel cell components, Fuel Cell. 8 (2008) 3–22.
[27] H.-W. Wu, A review of recent development: transport and performance modeling
of PEM fuel cells, Appl. Surf. Sci. 165 (2016) 81–106.
[28] J. Li, X. Li, Y. Zhao, W. Lu, Z. Shao, B. Yi, High-temperature proton-exchange-
membrane fuel cells using an ether-containing polybenzimidazole membrane as
electrolyte, ChemSusChem 5 (2012) 896–900.
[29] S. Subianto, Recent advances in polybenzimidazole/phosphoric acid membranes
for high-temperature fuel cells, Polym. Int. 63 (2014) 1134–1144.
[30] X. Tian, S. Wang, J. Li, F. Liu, X. Wang, H. Chen, D. Wang, H. Ni, Z. Wang,
Benzimidazole grafted polybenzimidazole cross-linked membranes with excellent
PA stability for high-temperature proton exchange membrane applications, Appl.
Surf. Sci. 465 (2019) 332–339.
[31] R.E. Rosli, A.B. Sulong, W.R.W. Daud, M.A. Zulkifley, T. Husaini, M.I. Rosli, E.
H. Majlan, M.A. Haque, A review of high-temperature proton exchange
membrane fuel cell (HT-PEMFC) system, Int. J. Hydrogen Energy 42 (2017)
9293–9314.
[32] S.S. Araya, F. Zhou, V. Liso, S.L. Sahlin, J.R. Vang, S. Thomas, X. Gao,
C. Jeppesen, S.K. Kær, A comprehensive review of PBI-based high temperature
PEM fuel cells, Int. J. Hydrogen Energy 41 (2016) 21310–21344.
[33] E. Quartarone, S. Angioni, P. Mustarelli, Polymer and composite membranes for
proton-conducting, high-temperature fuel cells: a critical review, Materials 10
(2017) 687–703.
[34] M. Ji, Z. Wei, A review of water management in polymer electrolyte membrane
fuel cells, Energies 2 (2009) 1057–1106.
[35] U.S. Department of Energy Hydrogen and Fuel Cells Program, Record 17007: Fuel
Cell Cost - 2017, http://www.hydrogen.energy.gov/program_records.html, 2017.
[36] G.J. Dahe, R.P. Singh, K.W. Dudeck, D. Yang, K.A. Berchtold, Influence of non-
solvent chemistry on polybenzimidazole hollow fiber membrane preparation,
J. Membr. Sci. 577 (2019) 91–103.
[37] P.M. Hergenrother, The use, design, synthesis, and properties of high
performance/high temperature polymers: an overview, High Perform. Polym. 15
(2003) 3–45.
[38] J.A. Asensio, E.M. Sánchez, P. Gómez-Romero, Proton-conducting membranes
based on benzimidazole polymers for high-temperature PEM fuel cells. A
chemical quest, Chem. Soc. Rev. 39 (2010) 3210–3239.
[39] P. Staiti, M. Minutoli, Influence of composition and acid treatment on proton
conduction of composite polybenzimidazole membranes, J. Power Sources 94
(2001) 9–13.
[40] M. Litt, R. Ameri, Y. Wang, R. Savinell, J. Wainwright, Polybenzimidazoles/
phosphoric acid solid polymer electrolytes: mechanical and electrical properties,
MRS Online Proc. Libr. 548 (1998) 313–323.
[41] M.A. Haque, A.B. Sulong, K.S. Loh, E.H. Majlan, T. Husaini, R.E. Rosli, Acid doped
polybenzimidazoles based membrane electrode assembly for high temperature
proton exchange membrane fuel cell: a review, Int. J. Hydrogen Energy 42 (2017)
9156–9179.
[42] J. Fontanella, M. Wintersgill, J. Wainright, R. Savinell, M. Litt, High pressure
electrical conductivity studies of acid doped polybenzimidazole, Electrochim.
Acta 43 (1998) 1289–1294.
[43] H. Steininger, M. Schuster, K. Kreuer, A. Kaltbeitzel, B. Bing枚l, W.H. Meyer,
S. Schauff, G. Brunklaus, J. Maier, H.W. Spiess, Intermediate temperature proton
conductors for PEM fuel cells based on phosphonic acid as protogenic group: a
progress report, Phys. Chem. Chem. Phys. 9 (2007) 1764–1773.
[44] Surya Subianto, Recent advances in polybenzimidazole/phosphoric acid
membranes for high-temperature fuel cells, Polym. Int. 63 (2014) 1134–1144.
[45] Z. Zuo, Y. Fu, A. Manthiram, Novel blend membranes based on acid-base
interactions for fuel cells, Polymers 4 (2012) 1627–1644.
[46] Q. Li, J.O. Jensen, R.F. Savinell, N.J. Bjerrum, High temperature proton exchange
membranes based on polybenzimidazoles for fuel cells, Prog. Polym. Sci. 34
(2009) 449–477.
E. Qu et al.
[47] X. Glipa, B. Bonnet, B. Mula, D.J. Jones, J. RozieÁre, Investigation of the
conduction properties of phosphoric and sulfuric acid doped polybenzimidazole,
J. Mater. Chem. 9 (1999) 3045–3049.
[48] A.Y. Leikin, E.G. Bulycheva, A.L. Rusanov, D.Y. Likhachev, High-temperature
proton-exchange membranes based on polymer-acid complexes, Polymer Science
48 (2006) 144–151.
[49] A. Schechter, R.F. Savinell, Imidazole and 1-methyl imidazole in phosphoric acid
doped polybenzimidazole, electrolyte for fuel cells, Solid State Ionics 147 (2002)
181–187.
[50] X. Wu, K. Scott, A H2SO4 loaded polybenzimidazole (PBI) membrane for high
temperature PEMFC, Fuel Cell. 12 (2012) 583–588.
[51] M.E. Schuster, T. Rager, A. Noda, K.D. Kreuer, J. Maier, About the choice of the
protogenic group in PEM separator materials for intermediate temperature, low
humidity operation: a critical comparison of sulfonic acid, phosphonic acid and
imidazole functionalized model compounds? Fuel Cell. 5 (2005) 355–365.
[52] J.-T. Wang, R. Savinell, J. Wainright, M. Litt, H. Yu, A H2O2 fuel cell using acid
doped polybenzimidazole as polymer electrolyte, Electrochim. Acta 41 (1996)
193–197.
[53] A. Kraytsberg, Y. Ein-Eli, Review of advanced materials for proton exchange
membrane fuel cells, Energy Fuels 28 (2014) 7303–7330.
[54] L. Vilčiauskas, M.E. Tuckerman, G. Bester, S.J. Paddison, K.-D. Kreuer, The
mechanism of proton conduction in phosphoric acid, Nat. Chem. 4 (2012)
461–466.
[55] Y.-L. Ma, J. Wainright, M. Litt, R. Savinell, Conductivity of PBI membranes for
high-temperature polymer electrolyte fuel cells, J. Electrochem. Soc. 151 (2004)
A8–A16.
[56] S. Authayanun, K. Im-Orb, A. Arpornwichanop, A review of the development of
high temperature proton exchange membrane fuel cells, Chin. J. Catal. 36 (2015)
473–483.
[57] C. Korte, F. Conti, J. Wackerl, W. Lehnert, Phosphoric acid and its interactions
with polybenzimidazole-type polymers, in: High Temperature Polymer
Electrolyte Membrane Fuel Cells, Springer, 2016, pp. 169–194.
[58] J. Wainright, J.T. Wang, D. Weng, R. Savinell, M. Litt, Acid-doped
polybenzimidazoles: a new polymer electrolyte, J. Electrochem. Soc. 142 (1995)
L121–L123.
[59] M. Hazarika, T. Jana, Proton exchange membrane developed from novel blends of
polybenzimidazole and poly(vinyl-1,2,4-triazole), ACS Appl. Mater. Interfaces 4
(2012) 5256–5265.
[60] S. Maity, T. Jana, Polybenzimidazole block copolymers for fuel cell: synthesis and
studies of block length effects on nanophase separation, mechanical properties,
and proton conductivity of PEM, ACS Appl. Mater. Interfaces 6 (2014)
6851–6864.
[61] J. Liao, J. Yang, Q. Li, L.N. Cleemann, J.O. Jensen, N.J. Bjerrum, R. He, W. Xing,
Oxidative degradation of acid doped polybenzimidazole membranes and fuel cell
durability in the presence of ferrous ions, J. Power Sources 238 (2013) 516–522.
[62] J. Yang, L. Qingfeng, J. Jens Oluf, P. Chao, N.C. Lars, J.B. Niels, H. Ronghuan,
Phosphoric acid doped imidazolium polysulfone membranes for high temperature
proton exchange membrane fuel cells, J. Power Sources 205 (2012) 114–121.
[63] J. Yang, Y. Xu, P. Liu, L. Gao, Q. Che, R. He, Epoxides cross-linked
hexafluoropropylidene polybenzimidazole membranes for application as high
temperature proton exchange membranes, Electrochim. Acta 160 (2015)
281–287.
[64] X. Li, X. Chen, B.C. Benicewicz, Synthesis and properties of phenylindane-
containing polybenzimidazole (PBI) for high-temperature polymer electrolyte
membrane fuel cells (PEMFCs), J. Power Sources 243 (2013) 796–804.
[65] H. Vogel, C.S. Marvel, Polybenzimidazoles, New thermally stable polymers,
J. Polym. Sci. 50 (1961) 511–539.
[66] E. Choe, Catalysts for the preparation of polybenzimidazoles, J. Appl. Polym. Sci.
53 (1994) 497–506.
[67] Y. Iwakura, K. Uno, Y. Imai, Polyphenylenebenzimidazoles, J. Polym. Sci., Part A:
Polym. Chem. 2 (1964) 2605–2615.
[68] P.E. Eaton, G.R. Carlson, J.T. Lee, Phosphorus pentoxide-methanesulfonic acid.
Convenient alternative to polyphosphoric acid, J. Org. Chem. 38 (1973)
4071–4073.
[69] D. Aili, L.N. Cleemann, Q. Li, J.O. Jensen, E. Christensen, N.J. Bjerrum, Thermal
curing of PBI membranes for high temperature PEM fuel cells, J. Mater. Chem. 22
(2012) 5444–5453.
[70] J. Park, L. Wang, S.G. Advani, A.K. Prasad, Mechanical stability of H3PO4-doped
PBI/Hydrophilic-Pretreated PTFE membranes for high temperature PEMFCs,
Electrochim. Acta 120 (2014) 30–38.
[71] A. Eguizábal, J. Lemus, V. Roda, M. Urbiztondo, F. Barreras, M.P. Pina,
Nanostructured electrolyte membranes based on zeotypes, protic ionic liquids
and porous PBI membranes: preparation, characterization and MEA testing, Int. J.
Hydrogen Energy 37 (2012) 7221–7234.
[72] F. Ublekov, H. Penchev, V. Georgiev, I. Radev, V. Sinigersky, Protonated
montmorillonite as a highly effective proton-conductivity enhancer in p-PBI
membranes for PEM fuel cells, Mater. Lett. 135 (2014) 5–7.
[73] S. Yu, H. Zhang, L. Xiao, E.W. Choe, B.C. Benicewicz, Synthesis of (2, 2′ - (1, 4-
phenylene) 5, 5′ -bibenzimidazole)(para-PBI) and phosphoric acid doped
membrane for fuel cells, Fuel Cell. 9 (2009) 318–324.
[74] R. He, L. Qingfeng, N.J. Bjerrum, Phosphoric acid doped AB-PBI membranes and
its applications in high temperature PEMFC, Chemical Journal of Chinese
Universities-Chinese 26 (2005) 2302–2305.
[75] H.J. Kim, S.Y. Cho, S.J. An, Y.C. Eun, J.-Y. Kim, H.-K. Yoon, H.-J. Kweon, K.
H. Yew, Synthesis of poly(2,5-benzimidazole) for use as a fuel-cell membrane,
Macromol. Rapid Commun. 25 (2004) 894–897.
18
Journal of Power Sources 533 (2022) 231386
[76] M.K. Daletou, N. Gourdoupi, J.K. Kallitsis, Proton conducting membranes based
on blends of PBI with aromatic polyethers containing pyridine units, J. Membr.
Sci. 252 (2005) 115–122.
[77] V. Di Noto, M. Piga, G.A. Giffin, E. Quartarone, P. Righetti, P. Mustarelli,
A. Magistris, Structure-property interplay of proton conducting membranes based
on PBI5N, SiO2-Im and H3PO4 for high temperature fuel cells, Phys. Chem. Chem.
Phys. 13 (2011) 12146–12154.
[78] L. Xiao, H. Zhang, T. Jana, E. Scanlon, R. Chen, E.W. Choe, L.S. Ramanathan,
S. Yu, B.C. Benicewicz, Synthesis and characterization of pyridine-based
polybenzimidazoles for high temperature polymer electrolyte membrane fuel cell
applications, Fuel Cell. 5 (2005) 287–295.
[79] S. Ghosh, S. Maity, T. Jana, Polybenzimidazole/silica nanocomposites: organic-
inorganic hybrid membranes for PEM fuel cell, J. Mater. Chem. 21 (2011)
14897–14906.
[80] S. Singha, T. Jana, J.A. Modestra, A.N. Kumar, S.V. Mohan, Highly efficient
sulfonated polybenzimidazole as a proton exchange membrane for microbial fuel
cells, J. Power Sources 317 (2016) 143–152.
[81] A. Sannigrahi, S. Ghosh, J. Lalnuntluanga, T. Jana, How the monomer
concentration of polymerization influences various properties of
polybenzimidazole: a case study with poly(4,4′ -diphenylether-5,5′ -
bibenzimidazole), J. Appl. Polym. Sci. 111 (2009) 2194–2203.
[82] J.A. Kerres, A. Chromik, K. Krajinovic, A. Katzfuss, C. Seyb, K. Aniol, V. Atanasov,
T. Kaz, T. Haering, A. Kruger, Monomers, polymers and cross-linked membranes
for membrane fuel cells and electrolysis, ECS Transactions 41 (2011) 1621–1632.
[83] J. Peron, E. Ruiz, D.J. Jones, J. Rozière, Solution sulfonation of a novel
polybenzimidazole, J. Membr. Sci. 314 (2008) 247–256.
[84] S.C. Kumbharkar, P.B. Karadkar, U.K. Kharul, Enhancement of gas permeation
properties of polybenzimidazoles by systematic structure architecture, J. Membr.
Sci. 286 (2006) 161–169.
[85] I. Cabasso, Y. Yuan, F.E. Johnson, Modified Polybenzimidazole (PBI) Membranes
for Enhanced Polymer Electrochemical Cells, Google Patents, 2006.
[86] J.A. Mader, B.C. Benicewicz, Sulfonated polybenzimidazoles for high temperature
PEM fuel cells, Macromolecules 43 (2010) 6706–6715.
[87] L. Wang, Z. Liu, J. Ni, M. Xu, C. Pan, D. Wang, D. Liu, L. Wang, Preparation and
investigation of block polybenzimidazole membranes with high battery
performance and low phosphoric acid doping for use in high-temperature fuel
cells, J. Membr. Sci. 572 (2019) 350–357.
[88] A. Sannigrahi, D. Arunbabu, R.M. Sankar, T. Jana, Tuning the molecular
properties of polybenzimidazole by copolymerization, J. Phys. Chem. B 111
(2007) 12124–12132.
[89] S.K. Kim, T.-H. Kim, T. Ko, J.-C. Lee, Cross-linked poly (2, 5-benzimidazole)
consisting of wholly aromatic groups for high-temperature PEM fuel cell
applications, J. Membr. Sci. 373 (2011) 80–88.
[90] P. Krishnan, J.-S. Park, C.-S. Kim, Performance of a poly (2, 5-benzimidazole)
membrane based high temperature PEM fuel cell in the presence of carbon
monoxide, J. Power Sources 159 (2006) 817–823.
[91] L. Xiao, H. Zhang, T. Jana, E. Scanlon, R. Chen, E.W. Choe, L.S. Ramanathan,
S. Yu, B.C. Benicewicz, Synthesis and characterization of pyridine-based
polybenzimidazoles for high temperature polymer electrolyte membrane fuel cell
applications, Fuel Cell. 5 (2005) 287–295.
[92] J.K. Kallitsis, M. Geormezi, S.G. Neophytides, Polymer electrolyte membranes for
high-temperature fuel cells based on aromatic polyethers bearing pyridine units,
Polym. Int. 58 (2009) 1226–1233.
[93] N. Esmaeili, E.M. Gray, C.J. Webb, Non-fluorinated polymer composite proton
exchange membranes for fuel cell applications-A review, ChemPhysChem 20
(2019) 2016–2053.
[94] S. Angioni, P.P. Righetti, E. Quartarone, E. Dilena, P. Mustarelli, A. Magistris,
Novel aryloxy-polybenzimidazoles as proton conducting membranes for high
temperature PEMFCs, Int. J. Hydrogen Energy 36 (2011) 7174–7182.
[95] J. Yang, R. He, Q. Che, X. Gao, L. Shi, A copolymer of poly[2,2′ -(m-phenylene)-
5,5′ -bibenzimidazole] and poly(2,5-benzimidazole) for high-temperature proton-
conducting membranes, Polym. Int. 59 (2010) 1695–1700.
[96] H.L. Lin, C.R. Hu, S.W. Lai, T.L. Yu, Polybenzimidazole and butylsulfonate grafted
polybenzimidazole blends for proton exchange membrane fuel cells, J J. Membr.
Sci. 389 (2012) 399–406.
[97] P. Ngamsantivongsa, H.L. Lin, T. Leon Yu, Properties and fuel cell applications of
polybenzimidazole and ethyl phosphoric acid grafted polybenzimidazole blend
membranes, J. Membr. Sci. 491 (2015) 10–21.
[98] J.A. Asensio, B. Salvador, G.-R. Pedro, Sulfonated poly(2,5-benzimidazole)
(SABPBI) impregnated with phosphoric acid as proton conducting membranes for
polymer electrolyte fuel cells, Electrochim. Acta 49 (2004) 4461–4466.
[99] D.C. Villa, S. Angioni, E. Quartarone, P.P. Righetti, P. Mustarelli, New sulfonated
PBIs for PEMFC application, Fuel Cell. 13 (2013) 98–103.
[100] H. Bai, W.S.W. Ho, New sulfonated polybenzimidazole (SPBI) copolymer-based
proton-exchange membranes for fuel cells, J. Taiwan Inst. Chem. Eng. 40 (2009)
260–267.
[101] S. Angioni, D.C. Villa, S.D. Barco, E. Quartarone, P.P. Righetti, C. Tomasi,
P. Mustarelli, Polysulfonation of PBI-based membranes for HT-PEMFCs: a possible
way to maintain high proton transport at a low H3PO4 doping level, J J. Phys.
Chem. A 2 (2014) 663–671.
[102] I. Nicotera, V. Kosma, C. Simari, S. Angioni, P. Mustarelli, E. Quartarone, Ion
dynamics and mechanical properties of sulfonated polybenzimidazole membranes
for high-temperature proton exchange membrane fuel cells, J. Phys. Chem. C 119
(2015) 9745–9753.
E. Qu et al.
[103] J.C. Tsai, C.K. Lin, Preparation of main-chain-type and side-chain-type sulfonated
poly(ether ether ketone) membranes for direct methanol fuel cell applications,
J. Power Sources 196 (2011) 9308–9316.
[104] X. Lin, X. Liang, S.D. Poynton, J.R. Varcoe, A.L. Ong, J. Ran, Y. Li, Q. Li, T. Xu,
Novel alkaline anion exchange membranes containing pendant benzimidazolium
groups for alkaline fuel cells, J. Membr. Sci. 443 (2013) 193–200.
[105] H.L. Lin, C.R. Hu, S.W. Lai, T.L. Yu, Polybenzimidazole and butylsulfonate grafted
polybenzimidazole blends for proton exchange membrane fuel cells, J. Membr.
Sci. 389 (2012) 399–406.
[106] J. Yang, D. Aili, Q. Li, Y. Xu, P. Liu, Q. Che, J.O. Jensen, N.J. Bjerrum, R. He,
Benzimidazole grafted polybenzimidazoles for proton exchange membrane fuel
cells, Polym. Chem. 4 (2013) 4768–4775.
[107] D. Wang, S. Wang, X. Tian, J. Li, F. Liu, X. Wang, H. Chen, T. Mao, G. Liu, Ethyl
phosphoric acid grafted amino-modified polybenzimidazole with improved long-
term stability for high-temperature proton exchange membrane applications, Int.
J. Hydrogen Energy 45 (2020) 3176–3185.
[108] J. Kerres, W. Cui, Acid-base Polymer Blends and Their Application in Membrane
Processes, US, 2001.
[109] C. Hasiotis, L. Qingfeng, V. Deimede, J.K. Kallitsis, C.G. Kontoyannis, N.
J. Bjerrum, Development and characterization of acid-doped polybenzimidazole/
sulfonated polysulfone blend polymer electrolytes for fuel cells, J. Electrochem.
Soc. 148 (2001) A513–A519.
[110] J. Kerres, A. Ullrich, Auml, T. Ring, Engineering Ionomeric Blends and
Engineering Ionomeric Blend Membranes, CA, 2004.
[111] J. Kerres, Applications of acid-base blend concepts to intermediate temperature
membranes, in: High Temperature Polymer Electrolyte Membrane Fuel Cells,
Springer, 2016, pp. 59–89.
[112] K.Y. Wang, Y. Xiao, T.S. Chung, Chemically modified polybenzimidazole
nanofiltration membrane for the separation of electrolytes and cephalexin, Chem.
Eng. Sci. 61 (2006) 5807–5817.
[113] D. Aili, Q. Li, E. Christensen, J.O. Jensen, N.J. Bjerrum, Crosslinking of
polybenzimidazolemembranes by divinylsulfone post-treatment for high-
temperature proton exchange membrane fuel cell applications, Polym. Int. 60
(2011) 1201–1207.
[114] J. Yang, Q. Li, L.N. Cleemann, J.O. Jensen, C. Pan, N.J. Bjerrum, R. He,
Crosslinked hexafluoropropylidene polybenzimidazole membranes with
chloromethyl polysulfone for fuel cell applications, Adv. Energy Mater. 3 (2013)
622–630.
[115] P. Ngamsantivongsa, H.-L. Lin, T.L. Yu, Crosslinked ethyl phosphoric acid grafted
polybenzimidazole and polybenzimidazole blend membranes for high-
temperature proton exchange membrane fuel cells, J. Polym. Res. 23 (2016) 22.
[116] M. Han, G. Zhang, Z. Liu, S. Wang, M. Li, J. Zhu, H. Li, Y. Zhang, C.M. Lew, H. Na,
Cross-linked polybenzimidazole with enhanced stability for high temperature
proton exchange membrane fuel cells, J. Mater. Chem. 21 (2011) 2187–2193.
[117] J.A. Kerres, Blended and cross-linked ionomer membranes for application in
membrane fuel cells, Fuel Cell. 5 (2005) 230–247.
[118] L. Wang, Z. Liu, Y. Liu, L. Wang, Crosslinked polybenzimidazole containing
branching structure with no sacrifice of effective N-H sites: towards high-
performance high-temperature proton exchange membranes for fuel cells,
J. Membr. Sci. 583 (2019) 110–117.
[119] X. Li, H. Ma, P. Wang, Z. Liu, J. Peng, W. Hu, Z. Jiang, B. Liu, Construction of
high-performance, high-temperature proton exchange membranes through
incorporating SiO2 nanoparticles into novel cross-linked polybenzimidazole
networks, ACS Appl. Mater. Interfaces 11 (2019) 30735–30746.
[120] H. Chen, S. Wang, J. Li, F. Liu, X. Tian, X. Wang, T. Mao, J. Xu, Z. Wang, Novel
cross-linked membranes based on polybenzimidazole and polymeric ionic liquid
with improved proton conductivity for HT-PEMFC applications, J. Taiwan Inst.
Chem. Eng. 95 (2019) 185–194.
[121] V. Sinigersky, D. Budurova, H. Penchev, F. Ublekov, I. Radev, Polybenzimidazole-
graft-polyvinylphosphonic acid-proton conducting fuel cell membranes, J. Appl.
Polym. Sci. 129 (2013) 1223–1231.
[122] P. Sun, Z. Li, L. Jin, S. Wang, X. Yin, Construction of proton channels and
reinforcement of physicochemical properties of OPBI/FeSPP/GF high
temperature PEM via building hydrogen bonding network, Int. J. Hydrogen
Energy 42 (2017) 14572–14582.
[123] P. Sun, Z. Li, L. Jin, Y. Yang, S. Wang, X. Yin, Y. Wang, Pre-oxidized acrylic fiber
reinforced ferric sulfophenyl phosphate-doped polybenzimidazole-based high-
temperature proton exchange membrane, Macromol. Mater. Eng. 302 (2017)
1600468–1600477.
[124] A. Chandan, M. Hattenberger, A. El-kharouf, S. Du, A. Dhir, V. Self, B.G. Pollet,
A. Ingram, W. Bujalski, High temperature (HT) polymer electrolyte membrane
fuel cells (PEMFC) - a review, J. Power Sources 231 (2013) 264–278.
[125] K.D. Kreuer, S.J. Paddison, E. Spohr, M. Schuster, Transport in proton conductors
for fuel-cell applications: simulations, elementary reactions, and phenomenology,
Chem. Rev. 104 (2004) 4637–4678.
[126] R. Haider, Y. Wen, Z.F. Ma, D.P. Wilkinson, L. Zhang, X. Yuan, S. Song, J. Zhang,
High temperature proton exchange membrane fuel cells: progress in advanced
materials and key technologies, Chem. Soc. Rev. (2021) 1138–1187.
[127] D.E. Smith, D.A. Walsh, The nature of proton shuttling in protic ionic liquid fuel
cells, Adv. Energy Mater. 9 (2019), 1900744-1900744.
[128] N. Esmaeili, E.M. Gray, C.J. Webb, Non-Fluorinated Polymer Composite Proton
Exchange Membranes for Fuel Cell Applications-A Review, ChemPhysChem
(2019) 2016–2053.
[129] D.W. Shin, M.D. Guiver, Y.M. Lee, Hydrocarbon-based polymer electrolyte
membranes: importance of morphology on ion transport and membrane stability,
Chem. Rev. 117 (2017) 4759–4805.
19
Journal of Power Sources 533 (2022) 231386
[130] J. Ran, L. Wu, Y. He, Z. Yang, Y. Wang, C. Jiang, L. Ge, E. Bakangura, T. Xu, Ion
exchange membranes: new developments and applications, J. Membr. Sci. 522
(2017) 267–291.
[131] L. Hong, B. Wang, C. Zhao, Phosphoric acid doped high temperature proton
exchange membranes based on comb-shaped polymers with quaternized graft
architectures, Appl. Surf. Sci. 483 (2019) 785–792.
[132] P. Xing, G.P. Robertson, M.D. Guiver, S.D. Mikhailenko, K. Wang, S. Kaliaguine,
Synthesis and characterization of sulfonated poly(ether ether ketone) for proton
exchange membranes, J. Membr. Sci. 229 (2004) 95–106.
[133] J. Jiang, X. Zhu, H. Qian, J. Xu, Z. Yue, Z. Zou, H. Yang, Cross-linked sulfonated
poly(ether ether ketone) electrolytes bearing pendent imidazole groups for high
temperature proton exchange membrane fuel cells, Sustain. Energy Fuels 3 (2019)
2426–2434.
[134] K. Raja, M. Raja Pugalenthi, M. Ramesh Prabhu, Investigation on SPEEK/PAI/
SrTiO3-based nanocomposite membrane for high-temperature proton exchange
membrane fuel cells, Ionics 25 (2019) 5177–5188.
[135] H. Bai, H. Wang, J. Zhang, J. Zhang, S. Lu, Y. Xiang, High temperature polymer
electrolyte membrane achieved by grafting poly(1-vinylimidazole) on polysulfone
for fuel cells application, J. Membr. Sci. 592 (2019) 117395.
[136] X. Ren, H. Li, K. Liu, H. Lu, J. Yang, R. He, Preparation and investigation of
reinforced PVP blend membranes for high temperature polymer electrolyte
membranes, Fibers Polym. 19 (2019) 2449–2457.
[137] S. Lu, R. Xiu, X. Xu, D. Liang, H. Wang, Y. Xiang, Polytetrafluoroethylene (PTFE)
reinforced poly(ethersulphone)-poly(vinyl pyrrolidone) composite membrane for
high temperature proton exchange membrane fuel cells, J. Membr. Sci. 464
(2014) 1–7.
[138] Z. Guo, X. Xu, Y. Xiang, S. Lu, S.P. Jiang, New anhydrous proton exchange
membranes for high-temperature fuel cells based on PVDF-PVP blended
polymers, J. Mater. Chem. 3 (2015) 148–155.
[139] N. Gourdoupi, A.K. Andreopoulou, V. Deimede, J.K. Kallitsis, Novel proton-
conducting polyelectrolyte composed of an aromatic polyether containing main-
chain pyridine units for fuel cell applications, Chem. Mater. 15 (2003)
5044–5050.
[140] H. Bai, H. Peng, Y. Xiang, J. Zhang, H. Wang, S. Lu, L. Zhuang, Poly(arylene
piperidine)s with phosphoric acid doping as high temperature polymer electrolyte
membrane for durable, high-performance fuel cells, J. Power Sources 443 (2019)
227219.
[141] K.S. Lee, J.S. Spendelow, Y.K. Choe, C. Fujimoto, Y.S. Kim, An operationally
flexible fuel cell based on quaternary ammonium-biphosphate ion pairs, Nat.
Energy 1 (2016) 16120.
[142] W. Wu, G. Zou, X. Fang, C. Cong, Q. Zhou, Effect of methylimidazole groups on
the performance of poly(phenylene oxide) based membrane for high-temperature
proton exchange membrane fuel cells, Ind. Eng. Chem. Res. 56 (2017)
10227–10234.
[143] J. Jang, D.-H. Kim, M.-K. Ahn, C.-M. Min, S.-B. Lee, J. Byun, C. Pak, J.-S. Lee,
Phosphoric acid doped triazole-containing cross-linked polymer electrolytes with
enhanced stability for high-temperature proton exchange membrane fuel cells,
J. Membr. Sci. 595 (2020) 117508.
[144] C.H. Tu, S.L.C. Hsu, E. Bulycheva, N. Belomoina, Novel crosslinked AB-type
polyphenylquinoxaline membranes for high-temperature proton exchange
membrane fuel cells, Polym. Eng. Sci. 59 (2019) 2169–2173.
[145] D. Henkensmeier, N.M.H. Duong, M. Brela, K. Dyduch, A. Michalak, K. Jankova,
H. Cho, J.H. Jang, H.-J. Kim, L.N. Cleemann, Q. Li, J.O. Jensen, Tetrazole
substituted polymers for high temperature polymer electrolyte fuel cells, J. Mater.
Chem. 3 (2015) 14389–14400.
[146] K.-D. Kreuer, Ion conducting membranes for fuel cells and other electrochemical
devices, Chem. Mater. 26 (2013) 361–380.
[147] O. Paschos, J. Kunze, U. Stimming, F. Maglia, A review on phosphate based, solid
state, protonic conductors for intermediate temperature fuel cells, J. Phys.
Condens. Matter 23 (2011) 234110.
[148] K. Firouz Tadavani, A. Abdolmaleki, M.R. Molavian, S. Borandeh, E. Sorvand,
M. Zhiani, Synergistic behavior of phosphonated and sulfonated groups on proton
conductivity and their performance for high-temperature proton exchange
membrane fuel cells (PEMFCs), Energy Fuels 31 (2017) 11460–11470.
[149] Y.Z. Meng, S.C. Tjong, A.S. Hay, S.J. Wang, Proton-exchange membrane
electrolytes derived from phosphonic acid containing poly(arylene ether)s, Eur.
Polym. J. 39 (2003) 627–631.
[150] E. Abouzari-Lotf, H. Ghassemi, S. Mehdipour-Ataei, A. Shockravi, Phosphonated
polyimides: enhancement of proton conductivity at high temperatures and low
humidity, J. Membr. Sci. 516 (2016) 74–82.
[151] T. Rager, M. Schuster, H. Steininger, K.D. Kreuer, Poly(1,3-phenylene-5-
phosphonic acid), a fully aromatic polyelectrolyte with high ion exchange
capacity, Adv. Mater. 19 (2007) 3317–3321.
[152] R. Hudson, R.Y. Adhikari, M.T. Tuominen, I. Hanzu, M. Wilkening,
S. Thayumanavan, J.L. Katz, Evaluation of carboxylic, phosphonic, and sulfonic
acid protogenic moieties on tunable poly(meta-phenylene oxide) ionomer
scaffolds, J. Polym. Sci., Part A: Polym. Chem. 57 (2019) 2209–2213.
[153] F.J. Pinar, P. Canizares, M.A. Rodrigo, D. Ubeda, J. Lobato, Titanium composite
PBI-based membranes for high temperature polymer electrolyte membrane fuel
cells. Effect on titanium dioxide amount, RSC Adv. 2 (2012) 1547.
[154] C. Yu-Nan Suryani, L. Juin-Yih, L. Ying-Ling, Polybenzimidazole (PBI)-
functionalized silica nanoparticles modified PBI nanocomposite membranes for
proton exchange membranes fuel cells, J. Membr. Sci. 403–404 (2012) 1–7.
[155] C.M. Chang, Y.L. Liu, Functionalization of multi-walled carbon nanotubes with
non-reactive polymers through an ozone-mediated process for the preparation of
E. Qu et al.
a wide range of high-performance polymer/carbon nanotube composites, Carbon
48 (2010) 1289–1297.
[156] Y. Devrim, H. Devrim, I. Eroglu, Polybenzimidazole/SiO2 hybrid membranes for
high temperature proton exchange membrane fuel cells, Int. J. Hydrogen Energy
41 (2016) 10044–10052.
[157] Y. Özdemir, N. Üregen, Y. Devrim, Polybenzimidazole based nanocomposite
membranes with enhanced proton conductivity for high temperature PEM fuel
cells, Int. J. Hydrogen Energy 42 (2017) 2648–2657.
[158] R. He, Proton conductivity of phosphoric acid doped polybenzimidazole and its
composites with inorganic proton conductors, J. Membr. Sci. 226 (2003)
169–184.
[159] A. Verma, K. Scott, Development of high-temperature PEMFC based on
heteropolyacids and polybenzimidazole, J. Solid State Electrochem. 14 (2010)
213–219.
[160] A. Shabanikia, M. Javanbakht, H.S. Amoli, K. Hooshyari, M. Enhessari,
Polybenzimidazole/strontium cerate nanocomposites with enhanced proton
conductivity for proton exchange membrane fuel cells operating at high
temperature, Electrochim. Acta 154 (2015) 370–378.
[161] Q. Liu, Q. Sun, N. Ni, F. Luo, R. Zhang, S. Hu, X. Bao, F. Zhang, F. Zhao, X. Li,
Novel octopus shaped organic-inorganic composite membranes for PEMFCs, Int.
J. Hydrogen Energy 41 (2016) 16160–16166.
[162] A. Gültek, M.G. İçduygu, T. Seçkin, Preparation and characterization of
polybenzimidazole-clay hybrid materials, Mater. Sci. Eng. B 107 (2004) 166–171.
[163] N. Üregen, K. Pehlivanoğlu, Y. Özdemir, Y. Devrim, Development of
polybenzimidazole/graphene oxide composite membranes for high temperature
PEM fuel cells, Int. J. Hydrogen Energy 42 (2017) 2636–2647.
[164] N. Guerrero Moreno, D. Gervasio, A. Godínez García, J.F. Pérez Robles,
Polybenzimidazole-multiwall carbon nanotubes composite membranes for
polymer electrolyte membrane fuel cells, J. Power Sources 300 (2015) 229–237.
[165] S. Lee, K. Seo, R.V. Ghorpade, K.-H. Nam, H. Han, High temperature anhydrous
proton exchange membranes based on chemically-functionalized titanium/
polybenzimidazole composites for fuel cells, Mater. Lett. 263 (2020) 127–167.
[166] G. Nawn, G. Pace, S. Lavina, K. Vezzù, E. Negro, F. Bertasi, S. Polizzi, V. Di Noto,
Nanocomposite membranes based on polybenzimidazole and ZrO\r2\r for high-
temperature proton exchange membrane fuel cells, ChemSusChem 8 (2015)
1381–1393.
[167] D. Aili, T. Allward, S.M. Alfaro, C. Hartmann-Thompson, T. Steenberg, H.
A. Hjuler, Q. Li, J.O. Jensen, E.J. Stark, Polybenzimidazole and sulfonated
polyhedral oligosilsesquioxane composite membranes for high temperature
polymer electrolyte membrane fuel cells, Electrochim. Acta 140 (2014) 182–190.
[168] S. Wang, F. Dong, Z. Li, Proton-conducting membrane preparation based on SiO2-
riveted phosphotungstic acid and poly (2, 5-benzimidazole) via direct casting
method and its durability, J. Mater. Sci. 47 (2012) 4743–4749.
[169] S.M. Haile, C.R.I. Chisholm, K. Sasaki, D.A. Boysen, T. Uda, Solid acid proton
conductors: from laboratory curiosities to fuel cell electrolytes, Faraday Discuss
134 (2007) 17–39.
[170] J. Piao, S. Liao, Z. Liang, A novel cesium hydrogen sulfate-zeolite inorganic
composite electrolyte membrane for polymer electrolyte membrane fuel cell
application, J. Power Sources 193 (2009) 483–487.
[171] Andreas Thess, Roland Lee, Crystalline ropes of metallic carbon nanotubes,
Science (1996) 483–487.
[172] N. Grossiord, J. Loos, O. Regev, C.E. Koning, Toolbox for dispersing carbon
nanotubes into polymers to get conductive nanocomposites, Chem. Mater. 18
(2006) 1089–1099.
[173] N.G. Moreno, D.F. Gervasio, A.G. Garcia, J.F.P. Robles, Polybenzimidazole-
multiwall carbon nanotubes composite membranes for polymer electrolyte
membrane fuel cells, J. Power Sources 300 (2015) 229–237.
[174] E. Abouzari-Lotf, M. Zakeri, M.M. Nasef, M. Miyake, P. Mozarmnia, N.A. Bazilah,
N.F. Emelin, A. Ahmad, Highly durable polybenzimidazole composite membranes
with phosphonated graphene oxide for high temperature polymer electrolyte
membrane fuel cells, J. Power Sources 412 (2019) 238–245.
[175] L.A. Utracki, Clay-containing polymeric nanocomposites and their properties,
IEEE Electr. Insul. Mag. 26 (2010) 6–15.
[176] D. Plackett, A. Siu, Q. Li, C. Pan, J.O. Jensen, S.F. Nielsen, A.A. Permyakova, N.
J. Bjerrum, High-temperature proton exchange membranes based on
polybenzimidazole and clay composites for fuel cells, J. Membr. Sci. 383 (2011)
78–87.
[177] K.S. Park, Z. Ni, A.P. Côté, J.Y. Choi, O.M. Yaghi, Exceptional chemical and
thermal stability of zeolitic imidazolate frameworks, Proc. Natl. Acad. Sci. U.S.A.
103 (2006) 10186–10191.
[178] Escorihuela Jorge, Sahuquillo óscar, B. García Abel, Giménez Enrique,
Compa Vicente, Phosphoric acid doped polybenzimidazole (PBI)/Zeolitic
imidazolate framework composite membranes with significantly enhanced proton
conductivity under low humidity conditions, Nanomaterials 8 (2018) 775.
[179] W.J. Phang, H. Jo, W.R. Lee, J.H. Song, K. Yoo, B.S. Kim, C.S. Hong,
Superprotonic conductivity of a UiO-66 framework functionalized with sulfonic
acid groups by facile postsynthetic oxidation, Angew. Chem. Int. Ed. (2015)
5142–5146.
[180] X.Y. Dong, J.H. Wang, S.S. Liu, Z. Han, Q. Tang, F.F. Li, S.Q. Zang, Synergy
between isomorphous acid and basic MOFs for anhydrous proton conduction of
low-cost hybrid membranes at high temperature, ACS Appl. Mater. Interfaces 10
(2018).
[181] S. Mukhopadhyay, A. Das, T. Jana, S. Das, Fabricating a MOF material with
polybenzimidazole into an efficient proton exchange membrane, ACS Appl.
Mater. Interfaces 3 (2020) 7964–7977.
20
Journal of Power Sources 533 (2022) 231386
[182] A. Schechter, F.S. Robert, Imidazole and 1-methyl imidazole in phosphoric acid
doped polybenzimidazole, electrolyte for fuel cells, Solid State Ionics 147 (2002)
181–187.
[183] F.J. Jiang, H.T. Pu, W.H. Meyer, Y.S. Guan, D.C. Wan, A new anhydrous proton
conductor based on polybenzimidazole and tridecyl phosphate, Electrochim. Acta
53 (2008) 4495–4499.
[184] Y. Dai, J. Wang, P. Tao, R. He, Various hydrophilic carbon dots doped high
temperature proton exchange composite membranes based on
polyvinylpyrrolidone and polyethersulfone, J. Colloid Interface Sci. 553 (2019)
503–511.
[185] H. Bai, H. Wang, J. Zhang, C. Wu, J. Zhang, Y. Xiang, S. Lu, Simultaneously
enhancing ionic conduction and mechanical strength of poly(ether sulfones)-poly
(vinyl pyrrolidone) membrane by introducing graphitic carbon nitride nanosheets
for high temperature proton exchange membrane fuel cell application, J. Membr.
Sci. 558 (2018) 26–33.
[186] L. Liu, Z. Li, Q. Che, Multilayered membrane electrolytes based on aramid
nanofibers for high-temperature proton exchange membrane fuel cells, ACS Appl.
Nano Mater. 2 (2019) 2160–2168.
[187] N. Mohammad, A.B. Mohamad, A.A.H. Kadhum, K.S. Loh, A review on synthesis
and characterization of solid acid materials for fuel cell applications, J. Power
Sources 322 (2016) 77–92.
[188] Q. Xie, Y. Li, J. Hu, X. Chen, H. Li, A CsH2PO4 -based composite electrolyte
membrane for intermediate temperature fuel cells, J. Membr. Sci. 489 (2015)
98–105.
[189] J. Xiong, Y. Huang, J. Li, L. Ma, G. Xu, Z. Liu, W. Cai, H. Cheng, A novel
thermomechanically stable LaF3CsH5(PO4)2 composite electrolyte with high
proton conductivity at elevated temperatures over 150 ◦ C, J. Energy Chem. 30
(2019) 114–120.
[190] V. Elumalai, S. Rathinavel, R. Annapooranan, M. Ganapathikrishnan,
D. Sangeetha, Phosphonated mesoporous silica based composite membranes for
high temperature proton exchange membrane fuel cells, J. Solid State
Electrochem. 23 (2019) 1837–1850.
[191] R.F. Hutzler, D.L. Meurer, K. Kimura, P.E. Cassidy, Synthesis and characterization
of polybenzazoles containing hexafluoroisopropylidene, High Perform. Polym. 4
(1992) 161–171.
[192] S.W. Chuang, S.L.C. Hsu, Synthesis and properties of a new fluorine-containing
polybenzimidazole for high-temperature fuel-cell applications, J. Polym. Sci., Part
A: Polym. Chem. 44 (2006) 4508–4513.
[193] Q.F. Li, H.C. Rudbeck, A. Chromik, J.O. Jensen, C. Pan, T. Steenberg,
M. Calverley, N.J. Bjerrum, J. Kerres, Properties, degradation and high
temperature fuel cell test of different types of PBI and PBI blend membranes,
J. Membr. Sci. 347 (2010) 260–270.
[194] H. Pu, L. Wang, H. Pan, D. Wan, Synthesis and characterization of fluorine-
containing polybenzimidazole for proton conducting membranes in fuel cells,
J. Polym. Sci., Part A: Polym. Chem. 48 (2010) 2115–2122.
[195] E. Abouzari-Lotf, H. Ghassemi, A. Shockravi, Novel Phosphonated poly(arylene
ether)s as potential high temperature proton conducting materials, Polymer 52
(2011) 4709–4717.
[196] J. Jalili, M. Geppi, V. Tricoli, Organic protic ionics based on Nitrilo
(trimethylenephosphonic acid) as water-free, proton-conducting materials,
J. Solid State Electrochem. 19 (2015) 1643–1650.
[197] X. Wu, Y.L. Hong, B. Xu, Y. Nishiyama, W. Jiang, J. Zhu, G. Zhang, S. Kitagawa,
S. Horike, Perfluoroalkyl-functionalized covalent organic frameworks with
superhydrophobicity for anhydrous proton conduction, J. Am. Chem. Soc. 142
(2020) 14357–14364.
[198] V. Atanasov, A.S. Lee, E.J. Park, S. Maurya, S.K. Yu, Synergistically integrated
phosphonated poly(pentafluorostyrene) for fuel cells, Nat. Mater. 20 (2021) 1–8.
[199] K.A. Perry, K.L. More, E.A. Payzant, R.A. Meisner, B.G. Sumpter, B.C. Benicewicz,
A comparative study of phosphoric acid-doped m-PBI membranes, J. Polym. Sci.,
Part B 52 (2014) 26–35.
[200] T.H. Kim, L. Tae-Wook, L. Jong-Chan, High-temperature fuel cell membranes
based on mechanically stable para-ordered polybenzimidazole prepared by direct
casting, J. Power Sources 172 (2007) 172–179.
[201] H.J. Kim, S.Y. Cho, S.J. An, Y.C. Eun, J.Y. Kim, H.K. Yoon, H.J. Kweon, K.H. Yew,
Synthesis of poly(2,5-benzimidazole) for use as a fuel-cell membrane, Macromol.
Rapid Commun. 25 (2010) 894–897.
[202] S.W. Chuang, L.C. Hsu, Synthesis and properties of a new fluorine-containing
polybenzimidazole for high-temperature fuel-cell applications, J. Polym. Sci., Part
A 44 (2006) 4508–4513.
[203] J. Lobato, C.i. Pablo, A.R. Manuel, Ú. Diego, F.J. Pinar, A novel titanium PBI-
based composite membrane for high temperature PEMFCs, J. Membr. Sci. 369
(2011) 105–111.
[204] M. Song, X. Lu, Z. Li, G. Liu, X. Yin, Y. Wang, Compatible ionic crosslinking
composite membranes based on SPEEK and PBI for high temperature proton
exchange membranes, Int. J. Hydrogen Energy 41 (2016) 12069–12081.
[205] M. Hu, T. Li, S. Neelakandan, L. Wang, Y. Chen, Cross-linked polybenzimidazoles
containing hyperbranched cross-linkers and quaternary ammoniums as high-
temperature proton exchange membranes: enhanced stability and conductivity,
J. Membr. Sci. 593 (2020) 117435.
[206] Y.m. zdemir, N. regen, Y. Devrim, Polybenzimidazole based nanocomposite
membranes with enhanced proton conductivity for high temperature PEM fuel
cells, Int. J. Hydrogen Energy 42 (2017) 2648–2657.
[207] C. Xu, W. Xu, W. Xu, M. Mamlouk, K. Scott, Composite membranes of
polybenzimidazole and caesium-salts-of-heteropolyacids for intermediate
temperature fuel cells, J. Mater. Chem. 21 (2011) 6014–6019.