Form Follows Function: a brief survey on the morphology of generic solvated

polymer electrolyte membrane

Gillian Kwan1 and Lauren Clark-Johnson2
1)
Department of Chemistry, Mount Holyoke College
2)
Department of Physics, Mount Holyoke College
To improve the performance of proton exchange membrane fuel cells (PEMFCs), the proton conduction
mechanism needs to be thoroughly understood. The proton conduction mechanism is dictated by the structure
of the membrane, therefore the elucidation of operating form of the polymer electrolyte membrane (PEM) is
the crucial first step to advancing fuel cell technology. A series of generic solvated bead-spring polymer were
simulated to explore the general hydrated morphology of polymer electrolyte membrane used in fuel cells.
Simulations were run using classical molecular dynamics program LAMMPS and its micelle tool. Structural
and potential parameters were varied in generic PEM systems to see their impact on phase segregations upon
coarse grained amphiphilic polymer molecules interaction with generic hydrophilic solvent. It was found
that an intermediate to high concentration of surfactant stabilizes the generic polymer membrane, as well
as longer surfactant chain length. These two factors help explain the popularity of Nafion, a sulfonated
polytetrafluoroethylene based polymer, as the standard in PEMs.

I. INTRODUCTION known as polymer electrolyte membrane fuel cells be-

A Lamborghini Aventador LP 700-4 can accelerate
from 0 to 100 km/h in just 2.9 seconds thanks to its
V12 petrol engine, which has a maximum power output
of 515 kW at 8250 rpm.1 The internal combustion en-
gine liberates the energy stored in fuel to do mechanical
work, thereby propelling the car to move. In spite of such
impressive speed, the V12 engine is subjected to Carnot
limitation as heat requires a temperature gradient, thus
limiting the maximum efficiency of the engine by the fac-
tor T1T−T 2
, which translates to about 15-20% efficiency
1
in real life.2 In addition, the car emits carbon dioxide at
a rate of 370 g/km.1 In wake of energy crisis and global
warming, there is not enough fossil fuels to spare or room
for more green house gases.
Fuel cell technology is a promising development for a
safe, environmental-friendly sustainable energy source.
Unlike a combustion engine, a fuel cell converts chem-
ical energy into electrical energy directly without pollu-
tants as by-products and its efficiency is not hindered by
Carnot limitation. The fuel cell uses an external supply
of chemical energy, usually hydrogen and oxygen, and can
operate indefinitely provided there is continuous supply
of hydrogen and its components are functional. All fuel
cells consists of a layer of electrolyte sandwiched between
an anode and a cathode; the reaction taking place inside
fuel cell is summarized in Equation 1.
Anode − 4H+ + 4e−
2H2 (g) →
Cathode O2 (g) + 4H+ + 4e− → − 2H2 O(`)
Overall 2H2 (g) + O2 (g) →
− 2H2 O(`) (1)
Fuel cells can be engineered to sizes ranging from small
handheld devices to power plants by varying the mate-
rial used for the electrolyte. The focus of this paper
are proton-conducting fuel cells, namely proton-exchange
membrane fuel cells (PEMFCs) and solid oxide fuel cells
(SOFCs). Proton-exchange membrane fuel cells are also
cause the electrolyte layer consists of a water-based,
acidic polymer membrane. The polymer material is com-
posed of hydrophilic segments that conduct ions, and hy-
drophobic segments that provide mechanical stability in
solution. PEMs operate at relatively low temperatures
(below 100◦ C) because proton conduction occurs via sol-
vation by water.3 SOFCs on the other hand operate be-
tween 800 and 1000◦ C for the ceramic solid electrolytes
do not become electrically and ionically active until such
high temperature range.4 These two types of fuel cells
are of particular interest because even though they em-
ploy similar mechanism to generate power, they operate
at the opposite ends of the fuel cell operation tempera-
ture scale. The optimal operating temperature obviously
depends on the characteristics of the electrodes and elec-
trolyte materials, which in turn are derived from their
molecular and atomic structures. The principle “form
follows function” was first coined by American architect
Louis Sullivan and became the defining pillar of mod-
ern architecture, but it is so universal that it extends to
chemical engineering as well.
It is the pervading law of all things organic
and inorganic,
of all things physical and metaphysical,
of all things human and all things superhu-
man,
of all true manifestations of the head, of the
heart, of the soul,
that the life is recognizable in its expression,
that form ever follows function.5
Following this principle, before investigating proton con-
duction mechanism in fuel cell electrolyte, we first need
to determine the “form” that allows such function. Such
task is relatively straightforward for SOFCs, as ceramic
solid electrolytes are normally mechanically robust and
they retain their main framework in their operating en-
vironment. However it is much more complex in PEM-
FCs because the membrane form that facilitates pro-

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ton conduction is very dynamic – so dynamic that there
exists a cornucopia of theories on the structure of hy-
drated perfluorosulfonic acid (PFSA) membrane, the pre-
dominant class of polyelectrolyte material in PEMFCs,
alone. These structural models arise from the complex
phase behavior of PFSA-water system, and they include
spherical water clusters, parallel cylindrical water chan-
nel networks, layered structures, polymer-bundles, and
polymer-ribbon models among many others.6–8 In con-
sidering a generic PEMFC, given the amphiphilic nature
of the polymer electrolyte, there is no surprise that phase
separation occurs when PEM is solvated. At high surfac-
tant concentration (as in PEM), the polymer molecules
self-assemble into micelles, aggregates in which the hy-
drophobic regions are sequestered from solvent by the
hydrophilic segments.9 This nanoscale phase segregation
resulting from surfactant interaction with solvent obvi-
ously alters the morphology of the membrane, which in
turn determines the transport properties.10
Previous simulation studies have attempted to elu-
cidate the morphology of solvated PEMs on various
levels of resolution, ranging from microscale atomistic-
quantum mechanical methods to mesoscale coarse-
grained methods.11 While atomistic simulations provide
detailed information on structures, they only apply to
local structures; extrapolating atomistic results to larger
scale simulations is not sensible as each scale is governed
by different laws of physics.12 Fortunately, the different
scales can be bridged by using a multi-scale approach,
which normally entails starting from atomistic level and
from that deriving a coarse grained model.13 An accu-
rate multi-scale modeling requires meticulous parameter-
ization of macroscopic properties, as degrees of freedom
increase in scaling-up.14 Fastidiousness aside, the multi-
scale approach seems to be the most appropriate method
in investigating the morphology of hydrated PEMs. How-
ever on the other hand, regardless of the precise morphol-
ogy of the solvated dynamic membrane and the actual
proton conduction mechanism, the fact that proton con-
ductivity depends on membrane hydration in all types
of PEMs that operate in temperature range of 60-90◦ C
establishes firmly that proton transport occurs within a
water network.2 In other words, atomistic scale details
notwithstanding, on the macroscopic level all PEMFCs
contain a water channel network of some sort as means
of proton conduction. Since the main goal of this pa-
per was to survey the structures that facilitate proton
conduction in PEMFCs in general, atomistic simulations
were both unnecessary and unfeasible for generic PEMs.
For these reasons, the investigation of proton conduc-
tion in PEMFCs was limited to the morphological aspect
only, specifically mesoscale simulations of water channel
topology. Such limitation emerged due to generic na-
ture of the system; quantitative characterizations such
as conductivity within membrane and proton conduc-
tion mechanism are impossible without explicit molecular
species. Unlike PEMFCs, there is no contention about
the structure of electrolytes in SOFCs, hence the proton
2
conduction mechanism can be investigated directly with-
out prior structure determination. As a side comparison
with PEM simulation, a few of the proton conduction
pathways of yttrium-doped BaZrO3 were inspected.
II. MOLECULAR MODELS AND METHODS
A. Simulation of PEMs
To understand the proton conduction mechanism in
polymer electrolyte membrane, simulation study requires
elucidation of the electrolyte structure in its operating
environment – the solvated membrane. Instead of mod-
eling Nafion, the archetypal PSFA membrane manufac-
tured by DuPont and the most popular material in PEM-
FCs, a generic surfactant is used so that an unbiased
exploration of PEM structure is possible. For faster
computational time, all simulation models were two-
dimensional; such simplification was acceptable for mod-
eling a thin PEM in a stacked membrane electrode assem-
bly. In order to function in a PEMFC, the membrane
material must meet the following criteria: i) high in-
trinsic proton conductivity; ii) long-term chemical, ther-
mal and mechanical stability; iii) impermeable to gases,
methanol, and contaminating ions.15,16 In this study, cri-
terion i was assessed by the shape and connectivity of
water channels formed in the membrane. Criteria ii and
iii were not evaluated as they were out of the scope of
this study.
The model The simulation box contained an initial
square lattice of solvents of the size 30 × 30Å, which was
then divided into smaller grids of length rlattice in which
molecules only interacted with other molecules that were
in the same or neighboring grids. rlattice was the square
root of the inverse of the number density of the sys-
tem (ρ∗ ). The actual box size was the product of ini-
tial square lattice of solvents and rlattice . The surfac-
tants were introduced to the system by replacing a cer-
tain number of solvents specified in the definition file. In
this coarse grained model, the generic surfactant-solvent
system was presented as a sequence of two-dimensional
beads. There were four types of beads: solvent (1), head
(2), tail (3) and tail (4). The non-bonded interactions
among them are summarized as follows: (a) solvent-
head, full-size and long-range; (b) tail-tail, size-averaged
and long-range; (c) solvent-tail, full-size and repulsive;
(d) head-tail, size-averaged and repulsive. These sites in-
teracted with one another via truncated Lennard-Jones
potential. Lennard-Jones potential is chosen because it
is the standard pairwise interaction potential for generic
systems; the potential is truncated because it is custom-
ary to establish a cut-off distance to conserve computa-
tional resources.17 The expression of Lennard-Jones 12-6
potential is given as
  
σ 12  σ 6
V (r) = 4ε − r < rc (2)
r r
 3

TABLE I: S0 Lennard-Jones potential parameters

Interaction Sites ε σ Cut-off

1-1 1.0 1.0 2.5
solvent-head 2-2 1.0 1.0 2.5
1-2 1.0 1.0 2.5
3-3 1.0 0.75 2.5
tail-tail 4-4 1.0 0.50 2.5
3-4 1.0 0.67 2.5
1-3 1.0 1.0 1.12246
solvent-tail
1-4 1.0 1.0 1.12246
2-3 1.0 0.88 1.12246
head-tail
2-4 1.0 0.75 1.12246

where r is the distance between sites, rc is the cut-off dis-

tance, ε is the well depth, and σ is the zero-crossing dis-
tance for the potential. Physically ε and σ are constants
characteristic of each Lennard-Jones system, in which ε
denotes the magnitude of attraction between two sites
and σ represents the maximum distance at which non-
bonded interaction remains zero between two sites. The
values of ε and σ were varied to see their impact on the
geometry of micelles. Although the Lennard-Jones po-
tentials defined for solvent molecules do not physically
correspond to water, for the purpose of this study the
solvent is regarded as interchangeable with water. The
system that served as the starting point was referred to as
System 0 (S0). The Lennard-Jones potential parameters
for S0 are listed in Table I. S0 had a number density of
0.7, 150 surfactants, and surfactant bond length of 0.75
in the units of σ (where 1 σ is equivalent to 1Å as per
program definition). Given the polymeric nature of sur-
factants, concentration is expressed in terms of weight
throughout this paper, with each bead weighing 1 mass
unit.
Molecular Dynamics theory and computational details
Simulations were run using classical molecular dynamics
program LAMMPS (Large-scale Atomic/Molecular Mas-
sively Parallel Simulator). Molecular Dynamics (MD)
is a statistical mechanics simulation technique in which
atomic trajectories within a system are calculated by
integrating Newton’s equation of motion at each time
step.18 Newton’s second law is given as follows:
d2 ri (t) ∂V
mi = Fi = − i = 1, ..., N
dt2 ∂ri
where ri is the position of particle i. From Equation 3,
it is clear that a function V (ri , ...rN ) representing the
potential energy of the system needs to be chosen prior
to simulation, as it is from this function that forces are
derived as gradients of potential with respect to rela-
tive coordinates of particles.19 As discussed previously,
Lennard-Jones 12-6 potential was the potential model of
choice.
Simulation systems were constructed using LAMMPS
tool micelle2d.f. Coordinates of the two-dimensional sys-
FIG. 1: A simplified scheme illustrating interactions in
MD simulation
tems were generated from running the definition file in
the Fortran-based program. The data containing the co-
ordinates were then read by a LAMMPS input script
for atom definition; but because the coordinates referred
to the positions of polymer beads rather than those of
atoms, FENE (finite extensible nonlinear elastic) poten-
tial was used to account for weighted pairwise energy and
force contributions from bonded atoms within each bead
molecule.20 The equation for FENE is
"
 2 #   
2 r σ 12  σ 6
E = −0.5KR0 ln 1 − + 4ε − +ε
R0 r r
(4)
where K is constant coefficient with the unit of en-
ergy per squared distance, and R0 is the maximum ex-
tent of the FENE bond. Each bead was connected to
one another via springs like in harmonic oscillators. A
schematic of the model is shown in Figure 1. Interac-
tions among beads were first computed using soft poten-
(3) tial push-off at fixed NVE condition, whose formula is
 
πr
E = A 1 + cos r < rc (5)
rc
This soft pairwise potential is also known as cosine po-
tential, in which A is a pre-factor. It is to clean up the
molecular topology, such as separate overlapping beads,
before the actual simulation.20 The soft potential was
computed for 1000 time steps, then the main computa-
tion with Lennard-Jones pairwise potential was run for
60000 timesteps.
 4

B. Simulation of SOFCs TABLE II: SE0 Lennard-Jones potential parameters

The tortuosity and porosity of PEMs attests to how Interaction Sites ε σ Cut-off
forms follow functions and vice versa. As a side com- 1-1 2.0 1.0 2.5
parison, a brief survey of proton conduction pathway in solvent-head 2-2 2.0 1.0 2.5
yttrium-doped barium metazirconate (YBaZrO3 ), a solid 1-2 2.0 1.0 2.5
ceramic electrolyte whose functional form has already 3-3 2.0 0.75 2.5
been elucidated, was conducted. tail-tail 4-4 2.0 0.50 2.5
Kinetic Monte Carlo method and computational de-
3-4 2.0 0.67 2.5
tails Although molecular dynamics can be used to com-
pute the dynamic evolution of the proton conduction in 1-3 0.75 1.0 1.12246
solvent-tail
YBaZrO3 , the time steps required for accurate simulation 1-4 0.75 1.0 1.12246
are usually of the order of femtoseconds (1×10−15 s), and head-tail
2-3 0.75 0.88 1.12246
because proton conduction proceeds on a much longer 2-4 0.75 0.75 1.12246
time scale, MD simulation of this scenario would require
infelicitously long computational time. Kinetic Monte
Carlo (KMC) is an algorithm that bypasses integration inefficient. S1 has the same potential and box size as
of motion along all time steps by considering transition does S0 but twice the number of surfactants, resulting
between states in a system directly.21 in a system with 60% surfactants and 40% solvent. As
The YBaZrO3 system contains 96 proton binding seen in Figure 2b, doubling the number of surfactants
sites and 48 redundant sites. The proton can move from 150 to 300 has lead to narrower water channels,
by (1) rotation; (2) intra-octahedral transfer; (3) and but the aggregates are still appearing to be distributed
inter-octahedral transfer. KMC computation was run at unevenly throughout the membrane. Based on this ob-
1000K starting at binding site 35 for 100 ps. Long range servation, a series of investigation in varying ε and σ was
pathways in trajectory were located using find program. conducted to see their impact on clusters formation. Fig-
ure 3a shows a modified S0 in which the attractive and
repulsive interactions have been made more extreme (the
III. RESULTS parameters are listed in Table II). This modified poten-
tial system is referred to as SE0, where E stands for
A. PEMs
epsilon. The VMD snapshot in Figure 3a shows that the
more extreme interactions among sites result in voids.
SE1 and SE2 are defined by the same set of potential
parameters as SE0, except the number of surfactants has
been changed from 150 to 300 and 500 respectively. From
Figure 3, it appears that increased surfactant concentra-
tion stabilizes the surface voids. However the surfactant
concentration of 78.9% in SE2 is too high that the wa-
ter channels are blocked. From these preliminary runs, it
could be gathered that the desirable number of surfactant
present in a functional PEM should be high enough to
stabilize strong site interactions, but not so high that the
surfactant clusters interrupt water clusters connectivity.
(a) S0 (b) S1

FIG. 2: Snapshots from VMD of the MD simulations of

S0 and S1. Solvent is represented by cyan beads, head
pink, tail 1 purple, and tail 2 lime for all systems in this
paper.

A snapshot from VMD of S0 is shown in Figure 2a.

The actual box size has expanded to 35.8569 × 35.8569Å
after simulation and contains 1200 molecules in total,
of which 62.5% by weight is solvent. At this hydra-
tion level, the surfactant concentration (37.5%) is too
low to delineate any water channels for more efficient
proton conduction. The broad and wide water networks
mean that protons could travel via myriad of pathways to
the cathode, which could be time-consuming and energy-
(a) SE0 (b) SE1 (c) SE2
FIG. 3: Comparison
Varying ε in SEs did not yield noticeable change in mi-
celles organization, so another series of simulation tests
were run (hence systems T). The T systems are derived
from SE1: they all contain 1500 molecules with an initial
 5

TABLE III: T Systems Lennard-Jones potential

parameters

Interaction Sites ε σ
T1 T2 T3 T4 T1 T2 T3 T4
1-1
solvent-head 2-2 3.0 3.0 3.5 5.0 1.0 0.5 1.0 1.0
1-2
3-3 0.75
tail-tail 4-4 3.0 3.0 3.5 5.0 0.50
3-4 0.67
1-3
solvent-tail 0.5 0.5 0.5 0.25 1.0 0.5 1.2 1.2
1-4 (a) Solvent-head interactions
2-3 0.88
head-tail 0.25 0.25 0.25 0.2
2-4 0.75
The cut-off values of T systems are virtually the same
as the previous systems, except rc were changed from
1.12246 to 2.5 for solvent-tail interactions in T3 and T4
to accommodate for a shift in equilibrium distance due
to a larger σ.

(b) Solvent-tail interactions

FIG. 5: Lennard-Jones potential plots

(a) T1 (b) T2
(c) T3 (d) T4
FIG. 4: Series T simulation snapshots
solvent square lattice of 30×30Å and a surfactant concen-
tration of 60%. The Lennard-Jones potential parameters
are cataloged in Table III, and the configurations of the
systems after MD simulations are included in Figure 4.
T1, T3 and T4 all exhibit leopard spots-like patterns in
their micelle arrangements, where as T2 shows a radi-
cally different topology. It is interesting to note that the
only potential parameter that is different in T1 and T2
is the σ corresponding to solvent-head interaction and
solvent-tail interaction. Comparing across the series, it
is observed that even though the values of ε become more
extreme in successive systems, T3 and T4 still retain the
same semblance as that of T1. While there appears to
be slight dimpling of the membrane with more extreme
parameterization of ε, there is no significant change in
the number of lone polymer chains (monomers) in these
three systems. Table III suggests that it is the sub-unity
values of σ in T2 that engender the void-riddled struc-
ture. To better understand the peculiarity of T2, con-
sider the Lennard-Jones potential plots of solvent-head
interactions and solvent-tail interactions in T systems
in Figure 5. (The Lennard-Jones potentials in tail-tail
interactions and head-tail interactions are omitted be-
cause the σ values do not vary across series.) Recalling
that rc = 2.5σ in all solvent-head interactions, Figure 5a
shows that the repulsion in T2 occurs at shorter range
due to a smaller value of σ. Consequently, despite that a
diminished magnitude of ε in T2, the long-range poten-
tial is more prominent, which explains the denser pack-
ing seen in Figure 4b. Similarly, the long-range potential
dominates in T2 in solvent-tail interactions as demon-
strated in Figure 5b. The repulsive force between hy-
drophobic tail sites and hydrophilic solvent sites in T2
occurs over the shortest range out of all, followed by that
in T1, then T3 and T4. In T2, the cut-off distance

is 21/6 , which is on the tail of the attractive force ap-
proximating London dispersion force. Again the negative
force contributes to larger micelle aggregates and fewer
monomers observed in this system. Even though the
irregularly shaped, holes-riddled membrane structure is
highly impractical in a fuel cell system, the denser pack-
ing and the more aligned, elongated micelle islands are
closer to the traits sought after in an ideal proton con-
ducting polyelectrolyte membrane, as they may delineate
solvent channels from surfactant chains for more direct
proton pathway.
(a) T2a (b) T2b
(c) T2c (d) T2d
(e) T2e (f) T2f
FIG. 6: Simulation snapshots of systems based on T2
The unusual feature of T2 led to another series of sim-
ulations based on the T2 potentials. The solvent density
of the systems were altered to see if porosity would be
lessened, and the series results are displayed in Figure 6.
The number density of solvent, ρ∗ , indicates that there is
a certain number of solvents per width of a solvent grid
squared, and that ratio is 0.7 for all systems considered
thus far. ρ∗ has been increased to 0.85 in T2a and 0.87
in T2b. The configurations in Figure 6a and Figure 6b
show greater continuous surface area as well as longer
micelle chains than T2, but there are slightly more in-
terstitial voids in these two systems. The numbers of
6
surfactants were reduced from 300 to 200 in the next two
trials to see if fewer polymer chains would prompt fewer
blocked water channels. T2c and T2d both have a sur-
factant concentration of 46%, which is 14% less than the
previous two; the former has the same number density as
T2a and T2b, while ρ∗ in the latter has been increased to
0.90. T2c In Figures 6c and 6d, the water channels seem
to be less congested, which is the desired result; how-
ever the micelle clusters are oriented in a more disorga-
nized fashion than in T2a and T2b, and the membranes
appear more fragmented as well. Once again fewer sur-
factants point to destabilization of the membrane, and
this condition combined with high number density may
have disturbed further the balance between surfactant
effect and long range interactions in these particular T2
potential systems. So far T2a is the best variant of T2,
and since improvement of T2a is not achieved by varying
number density or surfactant concentration, that leaves
bond length of surfactant as the remaining parameter to
be varied (initial solvent square lattice and number of
tails need to be kept constant for direct comparison with
its parent configuration T2). The bond length of surfac-
tants in T2e and T2f has been extended from 0.75Å to
1.0Å the number of surfactants is 300 in the former and
250 in the latter. Overall T2e in Figure 6e is not an im-
provement of T2a; in fact there are more discontinuities
of the membrane than its progenitor. A 6.4% decrease of
surfactant concentration lets T2f fare marginally better
out of the two, but its fragmentary character still proves
that it is not an improvement over T2a.
(a) TT0 (b) TT1 (c) TT2
FIG. 7: TT systems
The results from T and T2-related systems suggest
that a smaller σ would cause ellipsoidal micelles to adopt
a more prolate geometry, which may form alternating wa-
ter channels à la lamellar filters given an auspicious pa-
rameterization. Based on the aforementioned Lennard-
Jones potential plots, the value of σ = 0.5 in T2-type
systems may be too small that the membranes become
over constricted. In testing this hypothesis, another sys-
tems, called TT1 and TT2 are constructed and simu-
lated. The Lennard-Jones potential parameters for TT
systems (name stemming from the fact they are tests of
the previous trials) are identical to those defined for T2
systems, except σ in solvent-head and solvent-tail inter-
actions have been changed from 0.5 and 0.5 to 0.8 and
1 respectively. The difference among TT0, TT1 and
TT2 is that the surfactant bond length is 0.75Å 1.0Å
 7

TABLE IV: MT Lennard-Jones potential parameters the presence of an extra tail segment; the potential pa-
rameters for the MT systems are tabulated in Table IV.
Interaction Sites ε σ rc MT1 sees an increase of surfactants by 50 compared to
1-1 1.0 1.0 2.5 MT0; the initial solvent square lattice has also been en-
solvent-head 2-2 1.0 1.0 2.5 larged by 5Å to accommodate simulation error. MT2
1-2 1.0 1.0 2.5
was meant to be the system with further surfactant con-
centration increase than MT1, but due to programming
3-3 1.0 0.75 2.5
constraint, the number density was lowered from 0.7 to
4-4 1.0 0.50 2.5 0.65 instead. The simulation snapshots in Figure 8 show
tail-tail 5-5 1.0 0.25 2.5 a generally more promising class of micelle systems. A
3-4 1.0 0.67 2.5 direct comparison between MT0 in Figure 8a and its
3-5 1.0 0.34 2.5 2-tailed surfactant counterpart S1 in Figure 2b reveals
4-5 1.0 0.67 2.5 that the aggregates have not only grown in size due to
1-3 1.0 1.0 1.12246 extra tail segment in the former, but there also appears
solvent-tail 1-4 1.0 1.0 1.12246
to be some micelles amalgamated to form a large contin-
uous bulk. However, there also seems to be a moderate
1-5 1.0 1.0 1.12246
increase of monomers in MT0 relative to S1. Figure 8b
2-3 1.0 0.88 1.12246 suggests that while MT1 may have fewer numbers of
head-tail 2-4 1.0 0.75 1.12246 monomers, there seems to be less large micelle amalga-
2-5 1.0 0.62 1.12246 mation and more smaller micelles dispersed in the mem-
brane. This is most likely due to simulation box dilation
accompanying the minute increase in surfactant concen-
and 1.1Å respectively. 0.75Å is the typical bond length tration; even though there are more surfactants available
between two hydrogens, and extending the bond length for micellization, the expanded surface area discourages
in TT1 and TT2 is effectively moving away from the global agglomeration, hence there are more localized mi-
simplest diatomic bond towards a more realistic bond celles. MT2 mimics having higher surfactant concentra-
length for a coarse-grained polymeric system. Neverthe- tion by lowering its number density, and the aftermath of
less the new bond lengths are still considerably shorter lowered solvent density may be manifest in the dimpling
than an average carbon-carbon bond of 1.54Å.22 The sim- of the membrane seen in Figure 8c. The micelle clusters
ulation results seen in Figure 7 shows a vast diminution are connected to one another like a network, which is
of porosity in the TT systems. The micelle clusters are an arrangement sought after in forming water channels.
not aligned neatly, but there are canal-like expanses in However upon closer inspection, this surfactant network,
between micelles that could serve as proton conduction resembling branched nerves, bisects in a manner that
channels. obstructs direct proton transportation across the mem-
brane. Nevertheless, the MT systems are closest to the
theoretical configuration of a polymeric proton conduct-
ing membrane out of all trials.

(a) MT0 (b) MT1 (c) MT2 B. SOFCs

FIG. 8: VMD snapshots of MT systems. The

additional tail segment is represented by the color
mauve.
The last variable to be explored is surfactant chain
length. In MD simulations, this is achieved by insert-
ing more tail segments. For reason unbeknownst to the
author, simulations of systems with more than 3 tail seg-
ments were unsuccessful even after lengthy debugging
sessions. Because of this, only systems with 3 tail seg-
ments were simulated; these systems were later referred
to as MT, short for “micelle tails”. The basis system
MT0 has the same specifications as S1, plus additional
Lennard-Jones parameters that characterize the effect of
The average time in KMC simulation of proton conduc-
tion in YBaZrO3 was 0.21ps. Out of 205 possibilities, 2
of the proton conduction pathways found are pictured in
Figure 9. The pathway in Figure 9a shows proton mov-
ing through the perovskite oxide in a loop starting at
site H63 in a 10-step TRRTRTRRTR pathway, where T
and R stand for transfer and rotation respectively. Fig-
ure 9b shows proton migrating from site H43, moving in
a 20-step RRTTRTRRTRTRRTRTRTRT pathway that
eventually leads to the periphery of the unit cell towards
another image. The brief computation of the same sys-
tem was re-run at temperature 1200K, but since no sig-
nificant different pathways were found, the results are not
presented here.

(a) Proton pathway at displacement fraction 0.488585
(b) Proton pathway at displacement fraction 0.754597
FIG. 9: Proton conduction pathways of Y-doped
BaZrO3 . The light pink, red, green and blue atoms
represent hydrogen, oxygen, zirconium and yttrium
atoms respectively. The barium atoms are made
invisible for easier visualization.
IV. DISCUSSION
In parts of this section, the findings from this study
are considered in the context of hydrated Nafion mem-
8
brane in other computational investigations to see if the
archetypal fuel cell membrane maps onto our generic
results. The simulations of generic surfactant-solvent
PEMs were unsuccessful in finding a proton conducting
structure with distinct water channels, but the endeavor
was not unfruitful in that much useful information for
preliminary exploration of solvated PEM structures was
gleaned from the trials. The trials with S0, S1 and
SE systems demonstrate that there needs to be an ade-
quate amount of surfactants in a PEM fuel cell to provide
structural guidance for water channel formation as well
as membrane mechanical stability. The ideal percent-
age of surfactant by weight depends on the surfactant
size and the values of ε and σ Lennard-Jones parameters
that characterize the material, but based on the results
of this study it should be no less than 60% generally
speaking. This is a very loose estimate when compar-
ing with literature studies of solvated Nafion, in which
simulation systems contain water content no more than
20% by weight.23 However direct comparison between a
two-dimensional generic surfactant-solvent system and a
three-dimensional Nafion-water system is improbable, es-
pecially considering the particles in the generic system
all have mass of 1 molecular weight unit, and their inter-
atomic/intermolecular potentials do not correspond to
any actual physical substance that may be suitable for a
PEMFC. Nevertheless, this study does prove the concept
that there ought to be a high surfactant-to-solvent ratio.
The venture into exploring various ε and σ in the
Lennard-Jones potential yielded some bizarre morpholo-
gies of hydrated membranes seen in Figure 4b and Fig-
ure 6. While there exist too much interstitial holes, the
micelles are arranged in a manner akin to parallel chan-
nels. As discussed in the Results section, these interest-
ing features of these systems most likely arose from the
decreased value of σ in the solvent-head solvent-tail in-
teractions. The reduced σ values shift the potential curve
to the left, thereby making the long range attraction
much more dominant within the cut-off intermolecular
distance, which physically equate to very tightly packed
particles in the membranes. In Nafion, the Lennard-
Jones parameter σ for each atom is at least 3Å whereas
ε corresponding to each atom is on average fraction of
those in the T2 systems.24 Based on these values, the re-
duced σ in T2 systems is highly unlikely to correspond to
any physical occurring element. These Nafion Lennard-
Jones parameters would predict a membrane with more
dispersed micelles if the polymer chain were comprised
of only 3 segments. Just as a higher ratio of surfactant-
to-solvent can stabilize a membrane surface, so can the
extended length of surfactant tails, as demonstrated in
the MT systems in Figure 8. Since Nafion is normally
modeled as oligomers composed of at least ten monomer
units in simulation studies,24 interstitial gaps are rarely
observed.
The polymer electrolyte membrane is the heart of
membrane electrode assembly; it only conducts protons,
which forces electrons at the anode to travel through an

external circuit towards the cathode, generating electrical
power in the process.25 This selective permeability to pro-
tons prevents reactant crossover, which would result in
decreased fuel efficiency. Prevention of reactant crossover
is problematic in thinner PEMs, which are developed as
response to demand for mobile high power density fuel
cells. In slimming down PEM, the resistance through
the membrane is decreased and power output is thereby
amplified; but reduced resistance also leads to compro-
mise of mechanical durability and increased vulnerability
to reactant crossover.26 Furthermore, the water content
dependence of Nafion-type PEMFCs confines these fuel
cells to operate at conditions below 100◦ C which is in-
convenient for the automobile industries because the heat
management component would have to be cumbersomely
big to ensure uniform temperature distribution in the
fuel cell stack; in fact, the lower the operating temper-
ature, the larger the radiator needs to be.27 For these
reasons, alternatives to Nafion-type PEMs that operate
at elevated temperature are being developed. PEMFCs
that operate above 130◦ C have been reported to have
advantages of: (a) increased catalyst tolerance of impu-
rities; (b) simplification of water-management; (c) and
enhanced rejection of heat (thus reduction of radiator
size in automobiles).28 The proton conductivity in novel
PEMs is independent of water content, and the generic
system of this study should still be applicable to these
PEMs, it is just that the topology desired would differ
from that we look for in a PEMFC that utilizes water-
dependent proton conduction (vehicular mechanism).
The issue of temperature is one factor that was not
addressed in our study of generic PEM systems. The
generic system was not made to emulate any particular
type of PEMFCs (even though our interpretation of re-
sults have been leaning towards Naifon-type PEMFCS),
and the reduced Lennard-Jones units used throughout
simulations most likely would not correspond to oper-
ational temperature range of typical PEMs, integrating
temperature as a variable seems incompatible with the
goal of exploring polymer membrane without any spe-
cific chemical characteristics.
V. CONCLUSION
The morphology of solvated PEMs is indeed an elusive
subject; the difficulties encountered in this rudimentary
survey alone are already quite daunting, therefore it
is perfectly logical that there exists a multitude of
conflicting theories on hydrated Nafion membrane in
computational literature. Without obtaining the mem-
brane structure that facilitates proton conduction, there
is no way to study the proton conduction mechanism.
For a PEMFC that relies on water transportation of
protons, the hydrophobic phases in the membrane
should arrange themselves in a fashion that would de-
marcate water channels, hence maximizing water/proton
mobility for greater fuel cell efficiency. Nafion is known
9
to exhibit the most favorable proton/water mobility
due to its optimal polymer side chain length and
high water channel network connectivity. It is the
superior structural form that allows Nafion to perform
the function of proton conduction most efficiently in
the polytetrafluoroethylene-based membrane family.29
Conversely, it is the same structure that limits the PEM-
FCs to function at temperature below 100◦ C. On the
other end of operating temperature spectrum, the solid
crystallite structures of solid ceramic electrolytes require
operating temperature in the range of 800-1000◦ C to
reach a state that enables proton mobility. The low
operating temperature condition for PEMFCs makes
them ideal for mobile applications, where as the con-
tinuous heating implicit to high temperature activation
of conductivity for SOFCs relegates them to stationary
applications. From these two types of proton conducting
electrolyte fuel cells, we see concrete manifestation of
how forms and functions are interlinked.
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