Computational Materials Science 142 (2018) 122128

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Computational Materials Science

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

Proton conduction of fuel cell polymer membranes: Molecular dynamics

simulation
Zhonghao Rao , Chenyang Zheng, Fan Geng
School of Electrical and Power Engineering, China University of Mining and Technology, Xuzhou 221116, China

a r t i c l e i n f o a b s t r a c t

Article history: Fuel cell polymer membrane as the core of the proton exchange membrane fuel cell (PEMFC) plays an
Received 8 June 2017 important role in maintaining high intrinsic proton conductivity and insulating electrode. To investigate
Received in revised form 27 September the effect of crosslinking formation on proton conduction, the proton mobility and ion conduction were
2017
calculated and analyzed by using molecular dynamics (MD) simulation. As the crosslinking number
Accepted 29 September 2017
Available online 14 October 2017
increased, the proton diffusion coefficients increased at first and then decreased. The results indicated
that the formation of crosslinked bonds was beneficial for opening new channels to enhance the proton
conductivity. But too many crosslinking also can decrease proton diffusivity due to the blocking along the
Keywords:
Proton conduction
chain backbone. Besides, the proton conduction was better at 350 K than at 300 K. It can be concluded
Proton exchange membrane that temperature also had a significant impact on diffusivity and conductivity.
Crosslink 2017 Elsevier B.V. All rights reserved.
Molecular dynamics simulation

1. Introduction membrane doped with moderate polybenzimidazole (PBI) formed

PEM is the core of proton exchange membrane fuel cells
(PEMFCs) [1,2]. Proton conduction is the primary function of iono-
mer in the catalyst layers (CLs) of the polymer electrolyte fuel cell
[3,4]. In common CLs, commercial PEMs such as Nafion, Dow, Aci-
plex membranes were used widely, which have been investigated
widely. Many researchers [512] have studied the dynamic proper-
ties such as ion diffusion, proton conductivity and thermal proper-
ties such as thermal conductivity of PEM. Cui et al. [9] performed
classical MD simulations to analyze the effect of the length of the
side chain on hydrated morphology and hydronium ion diffusion
in Nafion and the SSC PFSA membranes. They concluded that the dif-
fusion coefficient of water and hydronium ions are both slightly
lower in the SSC PFSA membrane when compared to Nafion, which
can suggest that structural diffusion by proton hopping may account
for the observed higher conductivities in the SSC PFSA membrane.
To enhance the mechanical properties and improve conductivity,
the membranes were modified through experiment [1321] and MD
simulation [22] methods for further study. Han et al. [13] prepared a
series of novel organic-inorganic crosslinked hybrid proton
exchange membranes. The crosslinked hybrid membranes exhibited
excellent mechanical properties and high proton conductivity due to
the inorganic phase and crosslinked structure. Song et al. [14] pre-
pared acid-base ionic crosslinking sulfonated poly composite mem-
branes. Highly Sulfonated poly (ether ether ketone) (SPEEK)
Corresponding author.
E-mail address: raozhonghao@cumt.edu.cn (Z. Rao).
ionic crosslinking bonds which can improve conductivity, mechan-
ical strength and thermal stability. In addition to the experimental
method, Li et al. [22] prepared a novel polymer material which
was intended to be used as PEMs based on polynorbornenes via
ring-opening metathesis polymerization (ROMP) by MD simulation.
They investigated the feasibility of the designed structure mem-
brane by calculating the ion diffusion coefficient and proton conduc-
tivity. Kikugawa et al. [23] performed MD simulations on
amorphous polyethylene and polystyrene with varying crosslinking
concentrations to investigate the effect of crosslinking between
polymer chains and heat conduction. They revealed that crosslink-
ing has effect on thermal conductivity and the increase in thermal
conductivity was dominated by the contribution of energy exchange
by bonded interaction. Bahlakeh et al. [2426] employed MD simu-
lations to elucidate the effect of the degree of sulfonation (DS) on
structural and dynamical characteristics of SPEEK and sulfonated
poly (2,6-dimethyl-1,4-phenylene oxide) (SPPO) membranes at dif-
ferent temperatures. The simulated ionic conductivities had qualita-
tively agreement with the experimental data.
In our previous works [27], we investigated the proton mobility
and thermal conductivities of Nafion, Dow, and Aciplex mem-
branes. In this paper, we employed MD simulation to elucidate
the effect of crosslinking formation on proton diffusivity and con-
ductivity in PEM. We calculated the radial distribution functions
(RDFs), the coordination numbers (CNs), mean square displace-
ments (MSDs), and free volumes to gain a quantitative understand-
ing of the relationship between crosslinking and proton conduction
in the micro mechanism.

https://doi.org/10.1016/j.commatsci.2017.09.058
0927-0256/ 2017 Elsevier B.V. All rights reserved.
 Z. Rao et al. / Computational Materials Science 142 (2018) 122128 123

neutral and 900 water molecules to make water content k = 16

so that fuel cell in optimum operating condition. Fig. 2 is the initial
model schematic of the five simulation systems with crosslinking
number of 0, 5, 11, 20, 27, respectively, and named C0, C5, C11,
C20, C27, correspondingly.

2.2. Computational details

Fig. 1. Chemical structure of the membrane polymer.
In this article, the ab initio COMPASS force field [28] and three-
dimensional periodic boundary conditions were adopted. Firstly,
2. Models and computational details
the final structures obtained from the geometry optimization step
were heated from 200 to 500 K over a period of 500 ps in NPT
2.1. Models
ensemble and 1000 ps in NVT ensemble. The annealing procedure
was repeated five cycles. After that, using the final structures
All atomistic MD simulation models were carried out on manu-
obtained from the annealing procedure to perform the following
ally constructed 3D amorphous cells containing six polymer chains
dynamic simulation: 1000 ps NPT dynamics simulation and 2000
(the chemical structure of polymer as shown in Fig. 1, where takes
ps NVT dynamics simulation, which used to study the dynamic
x = 7 and n = 10), 60 hydronium ions in order to keep the cells
properties of these cells. In the simulation procedure, temperature

Fig. 2. The initial model schematic of C0, C5, C11, C20, C27 systems, corresponding (a)(e).
124 Z. Rao et al. / Computational Materials Science 142 (2018) 122128

Fig. 3. (a) Total potential energy and (b) temperature variation of the simulation
systems. Fig. 4. The radial distribution functions of SAOh at (a) 300 K, (b) 350 K.

Table 1 V nB
g A
B r  1
Densities of the crosslinked 0, 5, 11, 20, 27 systems at 300 and 350 K. NB 4pr 2 dr
Number of crosslinking Density (g cm
3) where nB is the number of B atoms situated at a distance r in a shell
300 K 350 K of thickness dr from particle A. NB and V represent the number of B
0 1.63 1.58 particles in the system and the total volume of the system, respec-
5 1.65 1.59 tively [32].
11 1.66 1.60 To evaluate the correlation of water molecules and hydronium
20 1.67 1.62
ions with sulfonic acid groups quantificationally, the coordination
27 1.69 1.63
number of these molecules around sulfur atoms were calculated by
using the following Eq. (2)[26]:
Z
was controlled by the Nose-Hoover method and pressure was con- NB
nB 4p r 2 g A
B rdr 2
trolled by the Berendsen method. The total potential energy and V
temperature variation of the simulation systems are shown in According to the well-known Einstein formula, in the MS soft-
Fig. 3. The fluctuations were slight and in the normal range which ware, the diffusion coefficient was calculated by the following
can be seen to the other significant of equilibrium [29]. The tem- equation [33]:
perature fluctuations and almost unchanged energy maybe caused * +
by the continuous transformation between kinetic energy and 1 XN
MSDt jri t
ri 0j2 3
potential energy [22]. Finally, the densities of all equilibrium sys- N i1
tems are listed in Table 1. For example, the density of C0 system
was 1.63 g cm
3 and 1.58 g cm
3 at 300 and 350 K, respectively, 1 dX
which showed good qualitative agreement with the experimental D limt!1 Nhjri t
r i 0j2 i 4
6N dt i!j
data [30]. And the densities of C0, C11, C20 and C27 systems were
1.65, 1.66, 1.67, 1.69 g cm
3 and 1.59, 1.60, 1.62, 1.63 g cm
3 at where D is the diffusion coefficient and N represents the number of
300 and 350 K, respectively. atoms moving diffusively in the system.
To analyze the interactions among different atoms such as the The obtained diffusion coefficients of hydronium ions were
sulfonate groups, hydronium ions, and water molecules in the used to calculate conductivity of hydronium ions according to Eq.
crosslinked membrane systems, several RDFs need to be calculated (4) [34].
by Eq. (1) [31].
 Z. Rao et al. / Computational Materials Science 142 (2018) 122128 125

Nz2 e2 D is maximum. This result was consistent with the SAOh radial dis-
r 5 tribution value in Nafion membrane [30]. The coordination num-
VkT
bers (CNs) of hydronium ions around the sulfur atoms which
where z, e and k are total charge in units of e, elemental charge and were obtained by integrating the area under the RDFs are shown
Boltzmann constant (k = 1.3806505  10
23 J K
1), respectively. N in Table 2. The CNs of hydronium ions around the sulfur atom at
is the number of hydronium ions, D is the diffusion coefficient of 300 K decreased from 2.24 for C0 system to 1.93 for C11 system
hydronium ions and T is the absolute temperature. and then increased to 2.19 for C27 system in the order of C0 >
C5 > C11 < C20 < C27, which was similar to the trends seen at
3. Results and discussion 350 K. The simulation of C0 system showed that the hydronium
ions stay closest to the sulfonate groups and C11 system stay far-
3.1. Radial distribution functions and coordination numbers thest which was meaning that C11 system membrane has the
strongest diffusion ability.
RDFs of sulfur atoms in ASO3 and the oxygen atoms in H3O+ for The RDFs between sulfur atoms in ASO3 and oxygen atoms in
different systems at 300 K and 350 K are shown in Fig. 4. We can H2O are displayed in Fig. 5. There are two peaks represented the
see from the Fig. 4, the first sharp peaks for temperature ranging first two hydration shells. Most hydronium ions resided in these
from 300 K to 350 K appeared at 3.71 , while the second broad two solvation shells, which lead to the locations of the two peaks
peaks appeared around 5.6 , which indicated that the possibility in the SAOw RDFs. The CNs of water molecules around the sulfur
of oxygen atom appearing at around 3.71 from the sulfur atom atom were in the opposite order with hydronium ions: C0 <
C5 < C11 > C20 > C27.
Table 2 To sum up, the CNs of the hydronium ions and of the water
Coordination numbers for Water (gSAOw(r)) and Hydronium Ion (gSAOh(r)) at 300 and molecules around the sulfur atoms at 350 K were smaller than
350 K.
those at 300 K for all systems. This trend was attributed to the
H3O+ H2O increased thermal transport and mobility at the higher tempera-
300 K 350 K 300 K 350 K ture by Venkatnathan et al. [30].
C0 2.24 2.11 5.81 5.46
C5 2.17 2.03 5.91 5.77
C11 1.93 2.02 7.68 6.59 3.2. Diffusivity and ion conductivity
C20 2.18 2.09 6.25 6.07
C27 2.19 2.06 5.38 5.59
To analyze the transport properties of the proton exchange
membrane and the mobility of the water molecules and of the
hydronium ions, we calculated the diffusion coefficients of hydro-
nium ions and water molecules for the vehicle mechanism at dif-

Fig. 5. The radial distribution functions of SAOw at (a) 300 K, (b) 350 K. Fig. 6. Mean square displacements of hydronium ion at (a) 300 K, (b) 350 K.
126 Z. Rao et al. / Computational Materials Science 142 (2018) 122128

ferent temperatures. Their MSD curves of water and hydronium

ion at 300 and 350 K are shown in Figs. 6 and 7, respectively.
The diffusion coefficients computed from the linear regime of the
MSD curves of water molecules and hydronium ions at different
temperatures are tabulated in Table 3. The diffusion coefficient
for hydronium ions is much smaller than that for water which
likely due to the electrostatic attraction between H3O+ and the
ASO
3.
For example, the diffusion coefficient of hydronium ions in
membrane at 300 K was 0.093  10
5 cm2 s
1 and at 350 K was
0.202  10
5 cm2 s
1 for C0 system, which were in qualitative
agreement with the published value (0.068  10
5 cm2 s
1 at
300 K and 0.229  10
5 cm2 s
1 at 350 K) [30]. The small difference
due to the MD simulation is basic on the statistic mechanics, the
system size and time step are all the influence factors of simulation
results. Thus, simulation time will be increased in the further work.
It can be seen that the formation of crosslinking had a signifi-
cant impact on the proton diffusion and ion conductivity and the
C11 system had the strongest proton diffusion ability. With the
increasing number of crosslinking, a peak value of the proton diffu-
sion and ion conductivity appeared, the new channel introduced by
crosslinked bonds may be the reason for this. Compared with the
non-crosslinked membrane, the introduction of crosslinked bond
provide a new channel which filled by water molecules to trans-
port the proton. Thus, introducing crosslinked bonds open new
channels, which directly contribute to the increase in proton diffu-
sion. On the other hand, the crosslinking could influence diffusivity
in not only positive ways but also in negative ways. That is to say,
the strong covalent bonds increased proton mobility between non-
bonded chain-segments, too many crosslinked bonds also can
decrease proton diffusivity due to the blocking along the chain
backbone. This was the reason for diffusivity decline later. Simi-
Fig. 7. Mean square displacements of water at (a) 300 K, (b) 350 K. larly, the proton diffusion coefficients had the same trend at 350
K and were larger than at 300 K. In addition, it can be seen from
the MSD curves that the influence of crosslinking at 300 K was
Table 3 more significant than at 350 K. It can be concluded that the effect
Diffusivity (cm2 s
1) and ion conductivity (S cm
1) at 300 and 350 K.
of temperature on proton exchange is greater than the crosslinked
Systems 105 D(H3O+) r bonds. Temperature also has a significant effect on the absolute
300 K 350 K 300 K 350 K value of the diffusion coefficients for both water and hydronium
ions.
C0 0.093 0.202 0.05 0.09
C5 0.106 0.268 0.052 0.095 Considering to the ions conductivity property in membrane sys-
C11 0.170 0.275 0.072 0.097 tem, the Einstein equation is valid. Thus the value of conductivity
C20 0.106 0.271 0.048 0.097 could be calculated for these systems. From Table 3, the ion con-
C27 0.102 0.270 0.045 0.096
ductivity of C0, C5, C11, C20, C27 systems are 0.05 (0.056 [22]),

Fig. 8. Connolly surface for (a) C11 system and (b) C27 system at 300 K.
 Z. Rao et al. / Computational Materials Science 142 (2018) 122128
Fig. 9. Free volumes for five systems at 300 and 350 K.
0.052, 0.072, 0.048, 0.045 S cm
1 at 300 K and 0.09 (0.077 [35]),
0.095, 0.097, 0.096 S cm
1 at 350 K, respectively, which had the
same regular and could be explained by the above explanation.
And all the systems meet the requirement of application in fuel
cells that proton conductivity needs to be higher than 0.05 S
cm
1 at room temperature [22].
The Connolly volume morphologies of proton exchange mem-
branes are shown in Fig. 8, which takes the typical systems of C0
and C11systems as examples. The blue part of the membrane sur-
face indicated the fractional free volume available for proton diffu-
sion. As the crosslinking number increased, the free volume value
increased at first and then decreased. The free volume values were
presented by histograms in Fig. 9, which can support the diffusivity
and ion conductivity results. This proved that the C11 membrane
system was more suitable for PEMFC operation.
4. Conclusions
In this paper, the models of hydrated membranes systems with
varying crosslinked degree were constructed to investigate the
effect of crosslinking formation on proton conduction. The proton
diffusivity and ion conductivity were calculated through analyzing
the MSDs, RDFs, the CNS, free volume values, etc. by molecular
dynamics method. With the increasing number of crosslinking, a
peak value of proton diffusion coefficients and conductivity
appeared. The new channel introduced by crosslinked bonds
was the reason for this. But too many crosslinking also can
decrease proton diffusivity due to the blocking along the chain
backbone. Besides, the PEMs had the better proton mobility at
350 K than at 300 K, which means that temperature also made a
significant impact on conductivity. Through researching the proton
diffusivity and conductivity, the micro-mechanism of hydrated
membranes systems with varying crosslinked degree was investi-
gated to provide the theoretical basis for the experiment to prepare
a series of polymer membrane with crosslinked bonds further.
Acknowledgements
This work was supported by the National Natural Science Foun-
dation of China (No. 51406223)
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