European Polymer Journal 114 (2019) 109–117

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European Polymer Journal

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

Preparation and performance of novel tetraphenylphosphonium- T

functionalized polyphosphazene membranes for alkaline fuel cells
⁎
Hongsa Han, Hongmei Ma, Jinghua Yu, Hong Zhu, Zhongming Wang
Faculty of Science, Beijing University of Chemical Technology, NO. 15 of North 3rd Ring East Road, Chaoyang District, 100029 Beijing, China

A R T I C LE I N FO A B S T R A C T

Keywords: A series of novel tetraphenylphosphonium cation-functionalized polyphosphazenes were successfully synthe-

Tetraphenylphosphonium salts sized and employed to prepare the corresponding anion exchange membranes. The typical properties of the
Anion exchange membrane prepared membranes for fuel cell including swelling ratio, water uptake, ion exchange capacity, tension test,
Polyphosphazene OH− conductivity and alkaline stability have been evaluated. PPMPP-3, one of the ionomer membranes with an
Alkaline stability
IEC value of 0.72 mmol g−1 displayed the hydroxide conductivities of 22.3 mS cm−1 at 80 °C, and showed
excellent alkaline stability that only 7.6% and 9.8% hydroxide conductivity degradation was observed after
being exposed to 1.0 M KOH at 60 °C and 80 °C for 10 days. The alkaline stability order of the AEMs studied in
this work was PPMPP-3 > PPMPP-4 > PPMPP-2 > PPMPP-1. This work provides a feasible method for en-
hancing the chemical stability of quaternary phosphonium salts which has a promising prospect to commercial
application of alkaline fuel cell.

1. Introduction
Currently, anion exchange membrane fuel cells (AEMFCs) have at-
tracted more and more attentions because they run under high-alkaline
conditions, which brings many advantages, e.g., satisfactory electrode
kinetics and acceptable manufacturing cost on account of operating
with non-platinum group electrocatalysts. However, as one of the core
components in AEMFCs, anion exchange membranes (AEMs) still face
some challenges such as low hydroxyl conductivity and poor alkaline
stability, which are related to the polymer backbones and functional
groups [1–4]. Various polymers, including polysulfone, polystyrene,
poly(phenylene), poly(ether ether ketone), poly(ether-imide), poly(aryl
ether ketone) and poly(2,6-dimethyl-1,4-phenyleneoxide)(PPO), have
been explored as main chains to carry functional groups [5–14].
However, these polymeric backbones may have some shortcomings
such as high rigidity, low density of functional groups, low water
sorption, or poor chemical stability [2,15,16,17]. How to design AEMs
based on appropriate backbones is an urgent task that needs to be
solved at the moment.
Polyphosphazenes are inorganic-organic composite polymers with a
linear backbone of alternating phosphorus and nitrogen atoms, each
phosphorus bearing two side organic substituents [18]. These polymers
have several advantages over the above polymers based on hydro-
carbon. Firstly, the P]N polymer backbone is highly flexible
benefitting from the absence of long range conjugation and low barrier
for free rotation around every repeating unit [19,20], which results in
excellent membrane-forming property. Secondly, the properties of the
prepared polymers are able to be finely modified by carrying out sub-
stitution reactions on the matrix macromolecular poly(dichloropho-
sphazene) (PDCP) [21]. The chlorine atoms contained in the polymer
are capable of being replaced with various sorts of organic functional
groups, providing a simple method for optimizing the chemical and
physical performance of the polymers [22,23]. As for AEMs, this ad-
vantage can lead to a high level of functionality per repeating unit and
unlimited possibility for side-group functionalization. The other ad-
vantage can be attributed to the remarkable chemical and thermal
stability of the polymer backbones [24]. Based on these advantages,
proton exchange membranes have already been prepared by carrying
acid groups on the polyphosphazene chain [25,26]. Recently, the ap-
plication of polyphosphazene has been further extended to AEMs by our
group [27,28].
In typical AEMs, to improve the hydroxide ion conduction from
cathode to anode, functional cation groups had better to tether cova-
lently on the polymer backbones to avoid the loss of cations. Generally,
cation groups such as quaternary ammonium, guanidinium, imidazo-
lium, benzimidazolium, quaternary phosphonium and metal-organic
coordination ions have been employed to carry on the polymer chains
[29–43]. However, under alkaline condition, these groups may be

⁎
Corresponding author.
E-mail address: wangzm@mail.buct.edu.cn (Z. Wang).

https://doi.org/10.1016/j.eurpolymj.2019.02.022
Received 26 October 2018; Received in revised form 23 January 2019; Accepted 18 February 2019
Available online 18 February 2019
0014-3057/ © 2019 Elsevier Ltd. All rights reserved.
H. Han, et al.
easily degradable, which results in the poor durability of AEMs. For
example, quaternary ammonium ions are unstable toward direct nu-
cleophilic substitution (SN2) and/or β-hydrogen (Hofmann or E2)
elimination under alkaline conditions at high temperature [44–46]. For
guanidinium and imidazolium cations, though they have resonant
structure with delocalized charge which is considered to stabilize both
cations, the durability of the corresponding AEMs were still not sa-
tisfactory according to the previous reports [47,48]. For guanidinium,
low energy barriers make it easy for the degradation to react under high
alkaline conditions. In most cases, the degraded products were urea
derivatives [47]. For common imidazolium, ring-opening reaction of
imidazole happens by the attack of hydroxyl ion at C2 position under
high pH conditions [48]. An efficient way to make imidazolium more
stable is to introduce substituents with different characteristics around
different positions of the imidazolium ring [49]. However, the alkaline
stability of AEMs is still a main challenge.
It is generally known that phosphonium salts favor the formation of
ylide upon interaction with strong alkalis by the Wittig-reaction me-
chanism, which is a usual strategy to synthesize alkenes. Nevertheless,
the above process frequently results in the loss of the phosphonium
cation [50]. The stability of quaternary phosphoniums is poorer under
high pH situation than that of quaternary ammoniums because qua-
ternary phosphorus atoms are much more electron-withdrawing com-
pared to quaternarized nitrogen, which makes α-H in the adjacent alkyl
groups more acidic and vulnerable to OH−. As a consequence, the at-
tack of hydroxyl can generate ylide intermediates (adjacent alkyl car-
banion and positive phosphonium) which have high reactivity [51].
Therefore, it may be reasonable to consider a phosphonium cation
without α-H atoms. Additionally, the protection of phosphonium ca-
tionic groups through the methods of increasing steric hindrance and
electron-donating effect are prospective ways to get stable [PR4]+ in
high pH environment: (i) effects of steric hindrance can make the cation
sites sterically crowded thereby the OH− access becomes much more
difficult, which improves the stability of phosphonium cation [16]; (ii)
substituent groups with electron-donating effect can increase the elec-
tron density on the cation site, depressing the electrostatic attraction,
which help stabilize the cations [41,51]. For example, Yan [52] re-
ported a type of AEMs prepared from tris(trimethoxyphenyl) phos-
phonium which exhibited good chemical stability and high ionic con-
ductivity, reaching 27 mS cm−1 at 20 °C. Coates [53] reported a tetrakis
(dialkylamino)phosphonium cation [P(N(Me)Cy)4]+ for AEMs. The
obtained AEMs showed excellent alkaline stability, stable for 140 days
in 15 M KOH at 22 °C and 25 days in 1 M KOH at 80 °C, respectively.
The degradation of tetrakis(dialkylamino)phosphonium cations was
also systematically explored in hydroxide or alkoxide anions after the
stability test [40].
Herein we reported a new class of hydroxide ion exchange mem-
brane based on polyphosphazene chain carrying tetraphenylpho-
sphonium cation. The structure of polyphosphazene ionomer has no α-
H around the tetraphenylphosphonium cation. It is expected that the
Wittig degradation of phosphonium cations can be inhibited under the
alkaline environment. Additionally, the large steric effect of phenyl
groups is helpful to the stability of tetraphenylphosphonium cation. The
membranes casted from the polyphosphazene ionomer have been pre-
pared and their performances for the application of fuel cells have been
studied. To consider the electronic effect of substituents, some groups
such as eH, eCH3, eCH3O, and eC(CH3)3 in tetraphenylphosphonium
cations have been investigated as well.
2. Experimental
2.1. Materials
Tetrahydrofuran (THF) and petroleum ether were supplied by
Beijing Chemical Works, refluxed with sodium for more than 48 h and
distilled. Hexachlorocyclotriphosphazene (HCCP, Beijing Datian
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European Polymer Journal 114 (2019) 109–117
Fengtuo Chemical Technology Co., Ltd.) was recrystallized from dry
petroleum ether before being used. 1,2,4-trichlorobenzene was dried by
distillation under reduced pressure over NaH and stored with activated
3A molecular sieves at 120 °C. Triphenylphosphine was purchased from
Tianjin Guangfu Fine Chemical Research Institute. Dichloromethane
(DCM) and nickel bromide were purchased from Beijing Coupling
Technology Co., Ltd. All other chemicals were purchased from
Sinopharm Chemical Reagent Co., Ltd. and used without further pur-
ification.
2.2. Synthesis of tetraphenylphosphonium cation and its derivatives
A series of tetraphenylphosphonium cations were synthesized via
nickel-catalyzed coupling reactions [54]. The procedure was given as
follows. Triphenylphosphine (15 mmol, 1.0 eq.) were mixed with 4-
bromophenol (16.5 mmol, 1.1 eq.), NiBr2 (0.75 mmol, 0.05 eq.) and
ethylene glycol (5 mL) in a 100 mL flask and heated at 180 °C for 3 h
under N2 atmosphere. After being cooled down to room temperature,
the mixture was diluted with DCM (50 mL), and the organic layer was
washed using deionized water (2 × 5 mL). After being dried with an-
hydrous Na2SO4 for 12 h, the organic mixture was filtered and con-
centrated by rotary evaporation. The obtained solid was washed using
diethyl ether (2 × 20 mL) and the final product was obtained as white
solid.
(4-Hydroxyphenyl)triphenylphosphonium Bromide (TPHP-1): yield,
91%. 1H NMR (400 MHz, DMSO‑d6) δ 11.38–11.05 (s, 1H), 8.01–7.91
(m, 3H), 7.86–7.76 (m, 6H), 7.67–7.75 (m,6H), 7.56–7.47 (m, 2H),
7.20–7.11 (m, 2H). 31P NMR (162 MHz, DMSO‑d6) δ 22.37, [M]+:
355.1246, found 355.1235.
(4-Hydroxyphenyl)tris(4-(methyl)phenyl) phosphonium Bromide
(TPHP-2): yield, 85%. 1H NMR (400 MHz, CD3OD) δ 7.64–7.58 (m, 2H),
7.52–7.47 (m, 6H), 7.46–7.40 (m,6H), 7.28–7.21 (m, 2H), 2.55–2.52
(m, 9H), 31P NMR (162 MHz, CD3OD) δ 21.72. [M]+: 397.1721, found
397.1718.
(4-Hydroxyphenyl)tris(4-(methoxy)phenyl) phosphonium Bromide
(TPHP-3): yield, 78%; 1H NMR (400 MHz, DMSO‑d6) δ 11.30–10.97 (s,
1H), δ7.57–7.52 (m, 2H), 7.50–7.43 (m, 6H), 7.26–7.22 (m,2H),
7.20–7.11 (m, 6H), 3.97–3.93 (s, 9H). 31P NMR (162 MHz, DMSO‑d6) δ
20.60. [M]+: 445.1569, found 445.1555.
(4-Hydroxyphenyl)tris(4-(tert-butyl)phenyl)phosphonium Bromide
(TPHP-4): yield, 59%. 1H NMR (400 MHz, DMSO‑d6) δ 11.32–11.03 (s,
1H), 7.73–7.67 (m, 6H), 7.66–7.61 (m, 2H), 7.54–7.45 (m, 6H),
7.28–7.23 (m, 2H), 1.42–1.36 (s, 27H), 31P NMR (162 MHz, DMSO‑d6)
δ 21.03. [M]+: 523.3130, found 523.3123.
Except the initial commercial material triphenylphosphine, some
other materials like tris(4-methyl)phosphine, tris(4-methoxyphenyl)
phosphane, tris(4-methoxyphenyl) phosphane and polyphosphazene
were synthesized and characterized. The corresponding information is
given in Supporting Information.
2.3. Preparation of polyphosphazene-based membranes
The polyphosphazene-based membranes were prepared according
to the following typical three-step procedure. Firstly, the potassium salt
was prepared by mixing (4-hydroxyphenyl)triphenylphosphonium
bromide, ethyl alcohol and K2CO3 (1.2 eq.). After stirring for 1 h at
25 °C, the mixture was filtered and concentrated by rotary evaporation,
then dissolved in DCM. After the insoluble substance was filtered out,
the organic product was concentrated again by rotary evaporation to
obtain the yellow pale potassium salt.
Secondly, the yellow pale potassium salt of quaternary phospho-
nium bromide (0.4 eq. of repeating units in polyphosphazenes) was
added to the THF solution of poly(dichlorophosphazene) (PDCP) and
stirred for 6 h at 65 °C. Then the mixture was added to the THF solution
(150 mL) containing 4-methyl-phenol sodium (1.6 eq. repeating unit in
polyphosphazenes), and stirred for further 48 h at 25 °C in N2
H. Han, et al.
atmosphere. The resulting solution was concentrated by rotary eva-
poration to obtain a sticky ionomer mixture. After being washed with
deionized water (2 × 100 mL) and petroleum ether (2 × 100 mL), the
final product tetraphenylphosphonium-functionalized polypho-
sphazene was obtained as off-white elastomer.
Finally, to cast the membrane, the off-white elastomer was dissolved
in THF, and the obtained solution (15 mL) was paved on a watch glass.
After being dried at 25 °C for 48 h, the membrane in bromide form was
obtained. To transfer the membranes into OH− form, the polymeric
membrane was immersed with 1.0 M KOH aqueous solution under N2
atmosphere for 48 h. The membrane was then washed for several times
using deionized water until the pH of lotion reached 6–7.
2.4. Characterization
2.4.1. Structural characterization
1 two-probe AC impedance method with the frequency range of 1–105 Hz
H and 31P NMR nuclear magnet resonance spectra were conducted
on a Bruker Avance III 500 spectrometer. The 31P NMR chemical shifts
were expressed as downfield from external 85% H3PO4. The attenuated
total reflection infrared (ATR-FTIR) spectra (4000–525 cm−1) were
recorded on a Nexues 8700 ATR-FTIR spectrometer. The high-resolu-
tion mass spectra (HRMS) were measured on an Agilent Technologies
6200 series TOF/6500 series with electron spray ion (ESI). The mole-
cular weight distribution was recorded by gel permeation chromato-
graphy (GPC, Agilent Technologies 1200 Series LC system) using DMF
with 2 wt% LiCl as the eluent at a flow rate of 1.0 mL min−1 in nitrogen
atmosphere, calibrated with a standard of polystyrene.
2.4.2. Thermal stability
A Mettler Toledo 1100SF thermogravimetric analyzer (Columbus,
OH) was used for the thermogravimetric analysis (TGA) of the samples
to study the thermal decomposition behavior of the prepared mem-
branes. The TGA measurements were conducted at temperatures from
40 to 800 °C at a heating rate of 10 °C min−1 with a nitrogen purge gas,
and the samples were dried in vacuum at 130 °C for 12 h before mea-
surement.
2.4.3. Water uptake and swelling ratio
The water uptake (WU) of the membranes was evaluated by the
mass changes before and after being soaked in deionized water. The
membranes were swollen in deionized water under ambient condition
for 24 h and then taken out. After the surface water was thoroughly
removed, the membranes were weighed immediately. The wet mem-
branes were dried in vacuum at 60 °C until a constant weight was ob-
tained. The WU was calculated as follow:
WU(%) = (Mw − Md )/Md × 100% (1)
where Md and Mw represent the masses of dry and wet membranes.
The swelling ratio (SR) was calculated as follow:
SR(%) = (Xw − X d)/X d × 100% (2)
where Xw and Xd are the lengths of the wet and the dry membranes,
respectively.
2.4.4. Ion exchange capacity
The ion exchange capacity (IEC) was calculated by applying the
classical back-titration method. The membranes were first ion ex-
changed by immersing in a KOH solution (1.0 M) at 25 °C for 48 h and
then thoroughly washed using deionized water to remove OH− by
physical adsorption. After that the membranes were soaked in a diluted
HCl solution (0.1 M, 50 mL) for 24 h. Finally, the HCl solution was ti-
trated with standard NaOH solution (0.1 M). The IEC values were cal-
culated as follow:
IEC (mmolg−1) = (VHCl × CHCl − VNaOH × CNaOH)/M (3)
where CHCl and CNaOH are the concentrations of HCl and NaOH
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European Polymer Journal 114 (2019) 109–117
solutions, VHCl and VNaOH stand for the volumes of the HCl and NaOH
solutions, respectively. M represents the weight of the membranes.
2.4.5. Mechanical properties
Tensile properties for PPMPPs membranes were determined with an
Instron Model 1185 instrument (25 °C and 50 ± 5% relative hu-
midity). According to the ASTM standard D882-02 using a crosshead
speed of 1 cm min−1, the PPMPPs with thickness of 90 μm were cut into
dumbbell-shaped samples with the area of 5 cm × 0.4 cm. The tensile
strength at break (Tsb) and elongation at break (Eb) were measured to
assess the mechanical properties of PPMPPs.
2.4.6. Ionic conductivity
The ionic conductivity of the membranes was determined by the
from 30 °C to 80 °C using an electrochemical workstation (Zahner
IM6ex, Germany). Before the ionic conductivity measurements,
PPMPPs were immersed with deionized water for several times to re-
move the residual KOH inside the membranes. The ionic conductivity σ
was calculated by
σ (S·cm−1) = d/(RA) (4)
where d, R and A represent the length of the membranes between the
anode and cathode (cm), the electric resistance value (Ω) and the in-
tersecting surface area of the membrane (cm2), respectively.
2.4.7. Chemical stability
The alkaline stability of the membranes was investigated by soaking
the membranes in a KOH solution (1.0 M) for 10 days at both 30 °C and
60 °C under N2 atmosphere. To evaluate the stability of PPMPPs, the
ionic conductivity was recorded every 48 h.
3. Results and discussion
3.1. Prepareation and characterization of tetraphenylphosphonium-
functionalized polyphosphazene membranes
Herein a series of novel mixed-substituent PDCP derivatives
(PPMPPs) were synthesized as shown in Scheme 1. After the prepara-
tion of PDCP [27], chloride atoms of PDCP in different percentages
were replaced by tetraphenylphosphonium cations, and the residual
chlorides in PDCP were replaced by 4-methylphenol anions. To ensure
good mechanical and chemical stability for PPMPPs membranes, the
residual phosphorus-chloride bonds had to be consume away because
they could cause crosslinking or instability in the polyphosphazene
backbones under alkaline condition [55]. After all membranes were
prepared, the number-average molecular weight (Mn) and weight-
average molecular weight (Mw) of PPMPPs were recorded by GPC:
PPMPP-1, Mn:121.8 kg mol−1, Mw:327.2 kg mol−1, Mw/Mn:2.68;
PPMPP-2, Mn:135.3 kg mol−1, Mw:331.2 kg mol−1, Mw/Mn:2.45;
PPMPP-3, Mn:136.7 kg mol−1, Mw:352.6 kg mol−1, Mw/Mn: 2.57;
PPMPP-4 Mn: 153.5 kg mol−1, Mw:377.3 kg mol−1 Mw/Mn:2.46. Ac-
cording to the GPC results, the molecular weight of all polymers
reached up to 105 order of magnitude, which met requirement of
membrane manufacture.
During the synthetic exploration, we tried to prepare some qua-
ternary phosphonium cations such as (4-hydroxyphenyl)tris(2,4,6-tri-
methylphenyl)) phosphonium and (4-hydroxyphenyl)tris(2,4,6-tri-
methoxyphenyl)) phosphonium, which have larger steric hindrance and
stronger electron donating effect than those general tetraphenylpho-
sphonium. It is a great pity that no desired products were founded be-
cause of various byproducts produced by the other side-reactions.
H. Han, et al.
Scheme 1. Synthetic route of tetraphenylphosphonium-functionalized polyphosphazene polymers.
3.2. Structure characterization
To confirm the structure of PPMPP-1, PPMPP-2, PPMPP-3 and
PPMPP-4 membranes, the ATR-FTIR spectra are shown in Fig. 1. It is
clear to observe that the absorption peaks around 3400 cm−1 are as-
cribed to the stretching vibration of OH−, indicating the successful
anion exchange of the ionomer membranes. The peak at 753 cm−1 is
attribute to P-C bond, and the absorptions at 831, 950 and 1203 cm−1
confirm the existence of P-O-C bonds, which indicates that some qua-
ternary phosphonium groups have carried on the polyphosphazene
backbones by phenol anion. The peak at 1250 cm−1 is ascribed to P]N
groups. In addition, adsorption peaks at 1396 and 1343 cm−1 in the
spectra of PPMPP-4 correspond to the tertiarybutyl groups. Totally,
these ATR-FTIR spectra data support the formation of membranes.
31
P NMR provided the structural information of the main chain and
side groups of the ionomers. According to the 31P spectrum of PPMPP-1
(Fig. 2), the element P in the membranes exists in five kinds of chemical
environment. The peaks at δ = −19.8 ppm and δ = −19.3 ppm are
attributed to the chemical shifts of the element P in P-(O-PhMe)2 and X-
P-O-PhMe (X = P+Ph4O−) groups, respectively. Considering the steric
hindrance of the tetraphenylphosphonium and 4-methylphenol, there
were also some incomplete-substituent P in the backbones. After the
Fig. 1. ATR-FTIR spectra of PPMPPs.
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European Polymer Journal 114 (2019) 109–117
membrane was immersed in aqueous KOH, the residual -Cl would be
replaced by eOH [15]. The peaks at δ = −16.8 ppm and
δ = −16.3 ppm are assigned to the chemical shifts of element P in HO-
P-O-PhMe and HO-P-X forms. The single peak with the chemical shift
+22.6 ppm is assigned to the P+ of tetraphenylphosphonium, which
indicates the successful incorporation of charged TPHP-1 groups into
the PDCP.
All the results from ATR-FTIR and 31P NMR provided the evidences
of the successful introduction of the functional tetraphenylpho-
sphonium groups in to polyphosphazene-based ionomers.
3.3. Thermal stability
The thermal stability of AEMs is a major concern in relation to their
application in AEMFCs. The thermal stability of PPMPPs membranes
and TPHP-1 was evaluated by TGA. As shown in Fig. 3, all the PPMPPs
membranes exhibit a two-step weight-loss behavior: The initial de-
gradation from 30 to 120 °C is ascribed to the residual water and or-
ganic solvent which are tightly bound inside the membranes after
drying in vacuum. The second stage of weight losing appears at
370–520 °C, which is related to the degradation of the polyphosphazene
ionomers. The degradation temperature of the TPHP-1 was around
400–500 °C, which almost coincided with the polymer backbones. All
the PPMPPs membranes exhibit excellent thermal stability below
370 °C. Totally, the thermal stability of membranes synthesized in this
work could fulfill the requirement of AEMFCs.
3.4. Mechanical properties of PPMPPs
AEMs should have sufficient mechanical strength if they are to be
used in AEMFCs. Generally, polyphosphazene membranes with suffi-
ciently high molecular weight possessed good mechanical properties.
Table 1 summarizes the mechanical properties of the PPMPPs. The
tensile strengths at break (Tsb), elongations at break (Eb) and Young’s
modulus of the membranes before stability test were in the range of
15.85–16.16 MPa, 7.6–9.1% and 0.34–0.48. After the PPMPPs were
soaked in 1 M KOH at 60 °C for 10 days, the Tsb values increased by
around 15%, and the Eb values decreased by a small margin, leading to
the increase of Young’s modulus. The result may relate to a slight de-
gree of crosslinking reactions occurred between some incomplete-
H. Han, et al. European Polymer Journal 114 (2019) 109–117

31
Fig. 2. P spectra of PPMPP-1.

Table 2
IEC, water uptake, and swelling ratio of membranes (t = 25 °C).
Samples Feed ratio* IEC (mmol g−1) WU (%) SR (%)

PPMPP-1–10 10% 0.27 ± 0.07 5.7 ± 1.2 2.2 ± 0.6

PPMPP-1–20 20% 0.50 ± 0.10 7.3 ± 0.7 3.1 ± 0.9
PPMPP-1–30 30% 0.73 ± 0.17 10.7 ± 2.6 6.0 ± 1.9
PPMPP-1 40% 0.75 ± 0.13 11.2 ± 1.7 6.1 ± 1.1
PPMPP-2 40% 0.73 ± 0.16 10.6 ± 2.8 5.9 ± 0.6
PPMPP-3 40% 0.72 ± 0.11 13.3 ± 0.8 6.8 ± 2.9
PPMPP-4 40% 0.75 ± 0.23 9.7 ± 3.1 5.7 ± 1.7

* Feed ratio: tetraphenylphosphonium equivalent of repeating unit in poly-

phosphazenes.

Fig. 3. TGA curves of PPMPPs and TPHP-1.

Table 1
Mechanical properties of the PPMPPs dry membranes before and after soaked in
1 M KOH at 60 °C for 10 days.
Membranes TSb (MPa) Eb (%) Young's modulus (GPa)

Before* After** Before* After** Before* After**

PPMPP-1 16.02 18.51 8.7 5.2 0.42 0.72

PPMPP-2 16.10 18.06 7.3 6.4 0.48 0.69
PPMPP-3 16.16 17.22 9.1 7.6 0.34 0.56
PPMPP-4 15.85 17.98 7.6 5.7 0.37 0.66

* Before: The membranes prepared in hydroxide form were dried in vacuum

at 60 °C until a constant weight was attained.
** After: The membranes prepared in hydroxide form were soaked in 1 M
KOH at 60 °C for 10 days, then were dried in vacuum at 60 °C until a constant
weight was attained.
substitute P atoms in polyphosphazene [25]. The mechanical properties
of the PPMPPs are still practicable to their application in AEMFCs.
3.5. IEC, water uptake, and swelling ratio of PPMPPs
The IEC value of the membranes is generally regarded as a crucial
influence factor for ion transfer, which acts as an indirect approximate
Fig. 4. Hydroxide conductivity of PPMPPs as a function of temperature.
quantity of the OH− conductivity. In the current study, IEC values of
PPMPPs were regulated by changing the substitute proportion of tet-
raphenylphosphonium on the parent macromolecular, PDCP. Various
equivalent of TPHP-1 (10%, 20%, 30% and 40% eq. of repeating unit in
polyphosphazenes) were introduced to the reaction system. All the
products were obtained as off-white elastomers. As shown in Table 2,
the tunable IEC values showed an increasing trend with the increasing
feed ratio of the charged TPHP-1. However, when the feed ratio reached
to 40%, the IEC of PPMPP-1 were not further improved. Even the re-
action time was up to 10 h, the IEC values were still around 0.7–0.8.

113
H. Han, et al.
Fig. 5. Hydroxide conductivity of PPMPPs at 80 °C as a function of Hammett
constants.
Fig. 6. Arrhenius plots of PPMPPs.
The real substitute ratio is about 25%∼30% of the repeating unite in
polyphosphazene (calculated according to the IEC values). When the
substitution reaction progressed to a certain degree, the large steric
hindrance of the tetraphenylphosphonium would make it difficult for
the follow-up tetraphenylphosphonium substitution reactions to occur.
Considering the experimental results, 40% feed ratio was regard as an
excess in the experiment. The same feed ratio was applied in the other
PPMPPs.
Generally, the water uptake (WU) and swelling ratio (SR) of AEMs
are in correlation with IEC values and dimensional stability. According
to Table 2, the increase in IEC leads to an increase in the hydrophilicity
of the membranes because water molecules trend to associate with the
charged functional groups. The highest WU value of all membranes is
around 10% at room temperature. The WU values of PPMPPs were
Fig. 7. Chemical stability of PPMPPs in 1.0 M KOH solution at 30 °C (a) and 60 °C (b).
114
European Polymer Journal 114 (2019) 109–117
lower than those of quaternary ammonium membranes because qua-
ternary phosphoniums have low hydrophilicity when compared to the
quaternary ammoniums in the similar structures [51]. In addition, low
water uptake of PPMPPs leads to low dimensional swelling. The water
swelling ratio of all membranes at 25 °C was less than 10%. Table 2 also
indicated the PPMPP-3 membranes had better hydrophilicity than that
of the other membranes. These results were due to the better hydro-
philicity of methoxyl derivatives TPHP-3.
3.6. Ionic conductivity of PPMPPs
The ionic conductivity of anion exchange membranes is a particu-
larly important intrinsic physical parameter. It is significantly influ-
enced by the IEC values. Fig. 4 demonstrates the ionic conductivities of
PPMPPs in the temperature range from 30 to 80 °C. From PPMPP-1-10
to PPMPP-1-30, ionic conductivities of the prepared membranes rise
gradually in conformity with the increase of IEC. The result is ex-
pectable as the concentration of active sites of anion transport increase.
Moreover, the ionic conductivity of PPMPPs at similar IEC values is also
evaluated and shown in Fig. 4 (from PPMPP-1 to PPMPP-4). The OH−
conductivities of obtained membranes reach 1.0 × 10−2 S cm−1 at
30 °C and increase to 2.0 × 10−2 S cm−1 at 80 °C, fulfilling the re-
quirement of AEMFCs. The results also revealed that the electron-do-
nating effect of the substituents in the functionalized tetraphenylpho-
sphonium cations is closely interrelated with OH− conductivity. The
PPMPP-3 exhibited the highest ionic conductivity with slightly low IEC
value. The result is ascribed to the strong electron-donating effect of
methoxyl groups, which makes the TPHP-3 possess higher electron
density on the cation site than that of the other three phosphonium
salts. The high electron density on the cation site greatly reduces the
electrostatic attraction between the positive and the negative ions,
which promotes the ionic mobility in the existence of a chemical or
electrochemical potential gradient [51]. Furthermore, the high WU% of
PPMPP-3 is another positive effect in the ionic conductivity.
The electron-donating property of substituent groups in the mole-
cule can also be assessed by Hammett constants [51]. The Hammett
constants order of the para-substituents studied in this work could be
eOCH3 > eC(CH3)3 > eCH3 > eH[56]. Fig. 5 present the resultant
ionic conductivity (at 80 °C) of PPMPPs as a function of corresponding
Hammett constants. The result revealed that the electron-donating
property and the ionic conductivity tend to correlate well. Electron-
donating property determined by Hammett constants of the substitutes
is an element that influences the ionic conductivity of the PPMPPs.
To study the effect mechanism of the obtained membranes,
Arrhenius plots for PPMPPs were estimated and shown in Fig. 6. On the
basis of the Arrhenius relationship between ionic conductivity and
working temperature, the activation energy for conduction (Ea) in
H. Han, et al. European Polymer Journal 114 (2019) 109–117

Table 3
Durability and conductivity of PPMPP-3 membrane compared to that of tetraphenylphosphonium-functionalized membranes reported in previous reports.
Membranes Alkali resistance OH− conductivity (mS cm−1) IEC (mmol g−1) Ref.

Test conditions Degradability

AEM8 unknown unknown 20.6 ± 3.1(90 °C) 0.45 [58]

[P(NR2)4]+ 2 M KOH/CH3OH, 80 °C unknown unknown unknown [40]
[P(N(Me)Cy)4]+ 1 M KOH, 80 °C, 140 d unknown 22 ± 1 (22 °C) unknown [53]
CQA-15 10 M NaOH, 80 °C, 200 h 60% 15.8 (20 °C) 1.00 [41]
PEEK-QPOH 1 M KOH, 60 °C, 48 h unknown 61 (20 °C) 0.89 [39]
PPMPP-3 1 M KOH, 60 °C, 10 d 7.6% 22.3 (80 °C) 0.72 ± 0.11 This work

31
Fig. 8. P spectra of TPHP-1 after immersed in 1.0 M KOH for 20 days at 30 °C.

Fig. 7 presents the resultant ionic conductivity ratios as a function of

Scheme 2. Decomposition mechanism of tetraphenylphosphonium in KOH
solution.
PPMPPs were measured respectively. The electron-donating effect is
considered to increase charge density and availably restrain the elec-
trostatic attraction, which could decrease the Ea values of the PPMPPs.
The result suggests that the PPMPP-3 membranes have the lowest Ea
value (14.54 kJ mol−1), and the none-substituded tetraphenylpho-
sphonium possessed the highest Ea value (15.06 kJ mol−1), respec-
tively.
3.7. Alkaline stability
High alkaline stability is one of the most desirable properties for
AEMs due to the high pH environments in operating AEMFCs. The al-
kaline stability of the prepared PPMPPs were investigated by immersing
the membranes in an aqueous KOH (1.0 M) solution at 30 °C and 60 °C
for 10 days. The ionic conductivity was recorded every 48 h at 80 °C.
alkaline ageing time.
Previous literature about the alkaline stability of benzyl quaternary
phosphonium demonstrated that AEMs based on benzyl quaternary
phosphonium tend to lose a significant percentage of functional groups
with the similar treatment at room temperature. This was ascribed to
the OH− attack on the labile α-H at the benzyl position [51]. In this
study, the benzyl group was replaced by phenyl group to weaken OH−
attack. It is observed that the ion conductivity of all PPMPPs did not
change significantly after immersion in the aqueous KOH (1.0 M) so-
lution at 30 °C even after 10 days of ageing (Fig. 7a). This result sug-
gests that the absence of α-H at the benzyl position has enhanced al-
kaline stabilities of P+ and demonstrated the positive effects in
PPMPPs.
However, ion conductivity of PPMPP-1 decreased obviously when
the test temperature increased to 60 °C (Fig. 7b). The ion conductivity
declined by 21.8% after 10 days ageing. When electron-donating effect
were introduced to weaken OH− attack, it was observed that the ionic
conductivities of PPMPP-2, PPMPP-3, PPMPP-4 were not changed as
serious as that of PPMPP-1. Base on the electron-donating effect of the
substituent groups, the alkaline stability of PPMPP-2 was better than
PPMPP-1. Specifically, 16.8% hydroxide conductivity degradation in
PPMPP-2 was observed after the testing period. Surprisingly, only 7.6%
hydroxide conductivity degradation in PPMPP-3 and 9.8% hydroxide
conductivity degradation in PPMPP-4 were observed. Moreover, when
increasing the temperature to 80 °C, the ionic conductivity degradation
of PPMPP-3 and PPMPP-4 were found to be 9.8% and 12.6% after
10 days, respectively. The alkaline stability of these membranes with
the different substituents indicated the electron-donating effect of p-

115
H. Han, et al.
31
Fig. 9. P spectra of TPHP-1 after immersed in 1.0 M KOH for 5, 10 and 15 days at 30 °C.
methylphenyl, p-methoxyphenyl and p-tertbutylphenyl could enhance
the alkaline stability of quaternary phosphonium compounds. The sta-
bilizing effect were consistent with the electron-donating effect.
Therefore, the alkaline stability order of the PPMPPs studied in this
work could be determined to be PPMPP-3 > PPMPP-4 > PPMPP-
2 > PPMPP-1.
Durability, conductivity and IEC values of various tetraphenylpho-
sphonium-functionalized membranes reported in literature were sum-
marized in Table 3. As illustrated in Table 3, the proposed membrane
exhibited excellent alkali stability as well as satisfactory OH− con-
ductivity and IEC values as the previously developed AEMs.
To further investigate the decomposition process of tetra-
phenylphosphonium, TPHP-1 was taken as a model. The decomposition
mechanism of TPHP-1 was discussed. In our research, after TPHP-1 was
immersed in 1.0 M KOH for 20 days at 30 °C, the 31P spectra of TPHP-1
and decomposition products were given in Fig. 8. The results were in
accordance with the reported in previous papers: The phosphonium
salts are decomposed by aqueous alkali to give tertiary phosphine
oxides and hydrocarbons [57]. The reported decomposition mechanism
was shown in Scheme 2. Though α-H was not existed in tetra-
phenylphosphonium, the P-C bones between P cations and phenyl
would break up leading to tertiary phosphine oxides. The peaks at
δ = +28.6 ppm and δ = +29.7 ppm were assigned to the decomposi-
tion products of TPHP-1 as shown in Fig. 8. Furthermore, the 31P NMR
spectra of TPHP-1 at different time of alkaline treatment was recorded.
According to Fig. 9, the phosphonium salt started to degrade from the
day of 15. The 31P spectra of TPHP-2, TPHP-3 and TPHP-4 at the end of
the alkaline test were also investigated (Fig. S2), and the results de-
monstrated the best stability of TPHP-3.
4. Conclusion
To sum up, a series of novel tetraphenylphosphonium salts were
designed, synthesized and employed in this study to prepare the cor-
responding anion exchange membranes. Compared with benzyl qua-
ternary phosphonium, the alkaline stability of tetraphenylphosphonium
salts is significantly enhanced, due to the absence of the labile α-H in
benzyl group. Furthermore, the results also revealed that the Hammett
constants of the substituent groups (eCH3, eOCH3, eC(CH3)3)
116
European Polymer Journal 114 (2019) 109–117
correlated well with the hydroxyl conductivity and the alkaline stability
of the cations. In addition, the prepared PPMPPs exhibited excellent
alkaline stability and satisfactory ionic conductivity in high pH en-
vironment under elevated temperatures. Hence, it is not difficult to see
that minimizing the electrostatic attraction by increasing electron
density of the cation site is pivotal for enhancing OH− conductivity and
alkaline stability of AEMs. These results indicate a possible and facile
strategy for improving the alkaline stability and OH− conductivity of
phosphonium cations and its promising application in commercial al-
kaline fuel cell.
Acknowledgment
The project is supported by the National Natural Science Foundation
of China (Grant Nos. 21776012 and 21276021).
NOTES
The authors declare no competing financial interest.
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.eurpolymj.2019.02.022.
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