INTERNATIONAL JOURNAL OF ENERGY RESEARCH

Int. J. Energy Res. 2011; 35:1213–1228

Published online 20 July 2011 in Wiley Online Library (wileyonlinelibrary.com). DOI: 10.1002/er.1889

REVIEW PAPER

A review on methanol crossover in direct methanol fuel

cells: challenges and achievements
Mahmoud Ahmed1,*,† and Ibrahim Dincer2
1
Department of Mechanical Engineering, Assiut University, Assiut 71516, Egypt
2
Faculty of Engineering and Applied Science, University of Ontario Institute of Technology (UOIT), 2000 Simcoe Street North, Oshawa,
Ontario L1H 7K4, Canada

SUMMARY
Direct methanol fuel cells have the potential to power future microelectronic and portable electronic devices because of
their high energy density. One of the major obstacles that currently prevent the widespread applications of direct methanol
fuel cells is the methanol crossover through the polymer-electrolyte membrane. Methanol crossover is closely related to
several factors including membrane structure and morphology, membrane thickness, and fuel cell operating conditions such
as temperature, pressure, and methanol feed concentration. This work presents a comprehensive overview of the state-of-
the-art technology for the most important factors, affecting methanol crossover in direct methanol fuel cells. In addition, the
current and future directions of the research and development activities, aiming to reduce the methanol crossover are
reviewed and discussed in order to improve the performance of direct methanol fuel cells. Copyright # 2011 John Wiley
& Sons, Ltd.

KEY WORDS
direct methanol fuel cells; methanol crossover; polymer-electrolyte membranes; methanol permeability

Correspondence
*Mahmoud Ahmed, Department of Mechanical Engineering, Assiut University, Assiut 71516, Egypt.
†
E-mail: aminism@aun.edu.eg

Received 2 March 2011; Revised 28 May 2011; Accepted 28 May 2011

1. INTRODUCTION Figure 1, consists of a flow field (including collector ribs

Fuel cells are nowadays one of the most promising clean en-
ergy technologies. Direct methanol fuel cells (DMFCs) have
the potential to power future microelectronic and portable
electronic devices. The direct methanol fuel cells offer some
advantages of effective operation at low temperatures, simple
design, and environmentally-benign nature. Moreover, meth-
anol is easier to handle because of its liquid nature at room
temperature. It is of low cost and availability at industrial scale
as well as easy to store, and safe in use and delivery. More
importantly, unlike hydrogen polymer exchange membrane
fuel cells, DMFCs based on methanol aqueous solution do
not need humidifying system and special thermal manage-
ment ancillary devices. In addition, the power and energy
densities are superior, even when compared with indirect fuel
cell and newly developed lithium-ion batteries. Possible
applications of the DMFC include video cameras, electric
wheelchairs, portable-powered briefcases, notebook compu-
ters, intelligent transportation systems (road signs, traffic
lights, etc.), and military communications [1–3].
In general, a fuel cell works by converting chemical en-
ergy of a fuel into electrical energy. DMFC, as shown in
and channels), a diffusion layer (DL), and a catalyst layer
(CL) on the anode and the cathode sides as well as a
polymer-electrolyte membrane (PEM). Reactants enter the
cell through the flow channels. The DL is typically made
of carbon cloth or paper, which not only tends to uniformly
distribute the reactants over the surface of the catalyst layers,
but provides an electrical connection between the CL and the
current collector as well. Electrochemical reactions occur in
the catalyst layers, which are attached to both sides of the
membrane. The catalyst layers must be designed in such a
manner to facilitate the transport of protons, electrons, and
reactants [4].
Typically, the liquid feed DMFC is operated at a tem-
perature lower than 100
C. The methanol feed solution is
forced to flow along the length of the flow channel and
to penetrate the DL to arrive at the anode CL, where the
methanol is electrochemically oxidized to form protons,
electrons, and CO2. The produced CO2 in the CL, then
moves backward through the DL to the flow channel, and
it is swept by the stream of liquid solution towards the exit
of the flow channel. The protons, formed at the anode CL,
are transported through ion-conducting polymer within the

Copyright # 2011 John Wiley & Sons, Ltd. 1213

M. Ahmed and I. Dincer
Figure 1. Schematic representation of the direct methanol fuel
cell (DMFC).
catalyst layers and the membrane to the cathode, where
they react with oxygen and electrons transported via the
external circuit to form water. The anode, cathode, and
overall cell reactions can be written as follows [5]:
Anode : CH3 OH þ H2 O ! 6Hþ þ 6e þ CO2
Cathode : 1:5 O2 þ 6Hþ þ 6e ! 3H2 O
Overall : CH3 OH þ 1:5O2 ! 2H2 O þ CO2
The most pressing problem associated with DMFC is that
of fuel crossover because of permeate methanol together with
water from the anode to the cathode side. Methanol crossover
during DMFC operation results in low power output because
of chemical oxidation of methanol at the cathode with the help
of the cathode catalyst, causing (1) electrode depolarization,
(2) mixed potential, resulting in the open-circuit voltage
(OCV) of the DMFC below 0.8V (3) consumption of O2,
(4) cathode catalyst poisoning by CO (an intermediate of
methanol oxidation), and (5) serious water accumulation on
the cathode (water being produced by methanol oxidation),
which limits O2 access to cathode catalyst sites. Moreover,
the overall fuel utilization efficiency of the fuel cell is low-
ered when there is excessive methanol crossover [6–8].
The objective of this review article is to present a compre-
hensive overview of the state-of-the-art technology for the
most important factors affecting methanol crossover in
DMFCs. In addition, the current and future directions of
the research and development activities that seek the
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Methanol crossover in direct methanol fuel cells
reduction in the methanol crossover to improve the DMFCs
performance are reviewed and discussed comprehensively,
and some potential solutions are also discussed.
2. CHALLENGES
Although considerable improvements in DMFCs design and
components have been made over the past years, numerous
challenging technical issues remain to be addressed before
the widespread commercialization of this type of fuel cell.
As previously reported, methanol crossover not only affects
the performance of DMFCs, but influences the volumetric
energy density of DMFCs as well. The transport of protons
takes place with water molecules, and for high-proton conduc-
tivity, PEM should be swollen enough with water, whereas it
should not for low methanol crossover. Methanol crossover
occurs by the absorption of methanol by membranes, diffusion
through membranes, and desorption from membranes. How-
ever, PEM, which satisfies both high-proton conductivity
and low-methanol crossover for DMFC, is not easily devel-
oped. Both proton conductivity and methanol permeability
increase with temperature. Concentration and rate of supplied
methanol affect methanol crossover. Increasing membrane
thickness reduces methanol crossover and increases the flow
resistance. Concentration and rate of supplied fuel/oxidant
affect methanol crossover [6,9]. These challenges and the
respective efforts carried out to reduce methanol crossover
in DMFCs are discussed in the current manuscript.
3. METHANOL CROSSOVER
When methanol comes into contact with the membrane, it
diffuses through the membrane from anode to cathode. It
is dragged along with the hydrated protons under the influ-
ence of electric current flowing across the cell. Hydraulic
pressure can also result in methanol transport. Therefore,
the methanol crossover through the membrane can be
driven by three transport mechanisms [10]: electro-osmotic
drag by proton transport, diffusion by methanol concentra-
tion gradient, and convection by the hydraulic pressure
gradient between the anode and the cathode. It was
reported that the diffusive mode of methanol transport
dominates when the cell is idle, whereas the electro-
osmotic drag dominates when the cell is operating [1].
When the convective and electro-osmosis drag modes are
neglected, methanol crossover occurs only because of diffu-
sion by methanol concentration gradient. In this case, the
methanol crossover can be defined by using the simple form
of Fick's law for diffusion across a membrane as follows:
dC
j ¼ D (1)
dz
where j is equal to the methanol flux, D is the diffusion coef-
ficient, C is the concentration of methanol, and z is the position
within the membrane. This equation can be integrated to yield.
Int. J. Energy Res. 2011; 35:1213–1228 # 2011 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Methanol crossover in direct methanol fuel cells
DH
j¼ ΔC
L perature and methanol feed concentration. In the next sec-
Here, H is the partition coefficient (or the ratio of con-
centration in the membrane to that in solution). L is the
thickness of the membrane, and ΔC is the concentration
difference between the solutions in contact with the mem-
brane. Methanol permeability (DH) is defined as the prod-
uct of the diffusion coefficient and partition coefficient and
takes into account both solubility and diffusion [11].
Direct methanol fuel cells are typically run under ambi-
ent conditions with a little or no pressure difference across
the cell so that the hydraulic permeation can be ignored. In
this case, the effect of convective transport through electro-
osmotic drag is considered in estimating methanol cross-
over. Equation (1) can be modified to incorporate the elec-
tro-osmotic drag [1] as follows:
dc
j ¼ D þcV
dz
where V is the convective velocity introduced by the pas-
sage of current and the effects of electro-osmotic drag. This
equation takes into account both diffusive and convective
contributions. The value of V can be defined as follows:
ED i M
V¼
θF
Here, ED is the electro-osmotic drag coefficient, i is the
current density, M is the methanol molar fraction at the in-
terface between the anode CL, and the membrane, F is
Faraday's constant, and θ is the volume fraction of metha-
nol within the membrane.
When all methanol crossover mechanisms are consid-
ered [10], the methanol crossover per unit area can be writ-
ten as
DHΔC C2 KΔP ED Mi
j¼ þ þ
L mL F orthosilicate (TEOS) and a variety of organic silane
where ΔC represents the difference between methanol con-
centration at the interface between the anode CL and the
membrane and between the membrane and the cathode
CL, respectively; ΔP is the difference in the liquid pressure
across the membrane. In addition, there are other several
mathematical formulas that are used in estimating the
methanol crossover [12–16].
Based on the above given equations (1– 4), the rate of
methanol crossover can be reduced by decreasing the dif-
fusivity, increasing the membrane thickness or reducing
the methanol concentration at the anode CL. The methanol
crossover is closely related to the methanol permeability,
and cell performance is directly related methanol cross-
over. Although the exact relationship between permeability
and methanol crossover is complex, several important fac-
tors are controlling methanol crossover. These factors in-
clude membrane material and morphology, membrane
Int. J. Energy Res. 2011; 35:1213–1228 # 2011 John Wiley & Sons, Ltd.
DOI: 10.1002/er
M. Ahmed and I. Dincer
thickness, and the cell operating parameters, such as tem-
(2)
tion, the influences of these factors on methanol crossover
are reviewed based on the previous published data and
their true interpretation.
4. FACTORS AFFECTING METHANOL
CROSSOVER
4.1. Membrane material and morphology
Because the methanol crossover causes considerable cell
voltage losses in the DMFC, different approaches to mini-
mize or eliminate methanol crossover have been carried
out such as: modification of Nafion membranes, using
new alternative types of proton-conducting membrane
materials, or exploring composite polymer materials.
Table I presents the development polymer-electrolyte
(3) membranes for the DMFCs that have been reviewed and
discussed in the present work. The reviewed polymer–
electrolyte membranes are classified into four categories
such as modified Nafion membranes, copolymer membranes,
blend membranes, and composite membranes.
Modified Nafion membranes. Nafion, a perfluorinated
sulfonic acid ionomer, has been the standard DMFC mem-
brane. It has a highly phase separated morphology that
impart excellent proton conductivity. On the contrary,
using Nafion in DMFC applications causes a relatively
high methanol crossover. Therefore, many modifications
of Nafion have been attempted to reduce the methanol
crossover. These include: palladium (Pd) impregnated
[17], laminating with poly(ethylene glycol)/silica (PEG/
SiO2) [18], polymerization [19–22], deposit Pd films on
the surface by sputtering [23], incorporating nano-
particles fillers into the polymers [24–26], casting
[27–33], silica coating [34], intercalation [35], composite
membrane [36–40], blending membranes with tetraethoxy
(4)
[41,42], high temperature processing [43], partial substitu-
tion of the sulfonic acid groups [44,45], and electrochem-
ical modification [46,47]. Unfortunately, decreasing
methanol permeability was always accompanied by a loss
in proton conductivity.
Copolymer membranes. A number of copolymer mem-
branes have been synthesized to reduce methanol crossover
and improve proton conductivity for DMFCs via partially
sulfonated [48–50], direct copolymerization [51–61], sul-
fonation [62–66], post sulfonation [67,68], the aromatic
nucleophilic polycondensation [69–73], plasma polymeri-
zation [74], and direct free radical polymerization [75].
Blend membranes. Blends research on polymer blends
includes partially sulfonated polymer blend [79], poly
(vinyl alcohol) and (sulfonated poly ether ether ketone)
SPEEK [80–82], poly(vinyl alcohol) crosslinked with
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M. Ahmed and I. Dincer Methanol crossover in direct methanol fuel cells

Table I. Developed polymer-electrolyte membranes for direct methanol fuel cells.

PEM Abbreviations Reference

Modified Nafion membranes

Pd nanophases in a Nafion polymer. Pd/ Nafion 17
Organic–inorganic hybrid-laminated Nafion 115. Nafion115/Hy 18
Nafion/polypyrrole composite. Nafion/P 19
Nafion/sulfonated phenol formaldehyde resin composite. sPFR/Nafion 20
Nafion/ crosslinked poly(2-Acrylamido-2-methyl-1-propanesulphonic acid). Nafion/AMPS 21
Nafion/polymerized dopamine nano-layer. Nafion 22
Pd-layered Nafion. Nafion117-Pd 23
Nafion/(3-mercaptopropyl) methyldimethoxysilane nanocomposite. Nafion/MPMDMS 24
Nafion/nano-size sulfated titanium dioxide solid superacid composite. Nafion/TiO2/SO42 25
Nafion/2-acrylamido-2-methylpropanesulfonic acid -modified montmorillonite. AMPS-MMT/Nafion. 26
Nafion–sulfonated organosilica nano-composite. Nafion/sDDS 27
Composite silica/Nafion. SiO2/Nafion 28
Polyimide/Nafion composite. PI/ Nafion 29
Nafion/acid functionalized zeolite beta nanocrystals nanocomposite. Nafion/AFB 30
Nafion/titanium dioxide Composite. Nafion/TiO2 31
Nafion/Nano-sized Fe2O3-SO24 solid superacid composite. Fe2O3/SO24/Nafion 32
Porous layered oxide/Nafion nanocomposite. Nafion/APO 33
Nano-silica layered Nafion composite. Nafion/silica 34
Nafion/organo-clay nanocomposite. Nafion/clay 35
Nafion/ternary composite materials. Nafion115/PI–PVA TSPS 36
Nafion/sol-gel-derived alkaline phosphate glass. STP/ Nafion 37
Nafion/zirconium meta-sulfonphenyl phosphonic acid-incorporated composite. Zr-msPPA/Nafion 38
Nafion/polyphenylene oxide with phosphomolybdic acid (PMA) composite. Nafion/PPO-PMA 39
Nafion/poly(diallyldimethylammonium)/PM multilayer films. PDDA/PM/ Nafion 40
Blended Nafion/Sulfonated poly(ether ether ketone)s. Nafion/SPEEK 41
Nafion/ORMOSIL hybrid. TEOS/DEDMS 42
Heat-treated Nafion. HTN 43
Nafion/sulfated b-cyclodextrin composite. Nafion/sb-CD 44
Blended Nafion/sulfonated poly(ether ether ketone). Nafion/SPEEK 45
Organic silica/Nafion composite. Nafion /SILCPM 46
Nafion/polyaniline. Nafion /PA/PY 47
Copolymer membranes
Partially sulfonated polystyrene block poly(ethylene -ran-butylene) SSEBS 48
block polystyrene copolymers.
Partially sulfonated block copolymers. SEBS 49
Disulfonated poly(arylene ether benzonitrile) Copolymers. 6FCN-35/BPSH-40 50
Sulfonated co-polyimide. Co-SPIs 51
Sulfonated polyimides. SPI 52
Sulfonated naphthalene dianhydride based polyimide copolymers. BAPS/ ODA 53
sulfonated poly(phthalazinone ether sulfone). SPPES 54
Sulfonated cardo poly(aryl ether sulfone). SPES-C 55
Sulfonated naphthalenic polyimides. SPI-K 56
Crosslinked sulfonated poly(arylene ether ketone) (SPAEKs). SPAEKs 57
Epoxy-based cross-linked sulfonated poly(arylene ether ketone). Cr-SPAEK 58
New comb-shaped poly(arylene ether sulfone) copolymers. S-PAES 59
Crosslinked sulfonated poly(arylene ether sulfone). C-ABPSH40 60
Sulfonated poly(arylene ether ketone) copolymers. C-SPAEK 61
Sulfonated polyethersulfone Cardo. SPES-C 62
A triblock copolymer ionomer, sulfonated poly(styrene-isobutylene-styrene). S-SIBS 63
Sulfonated polyimide*. NTDA/DAPPS/ODA 64
Sulfonated poly(styrene-b-butadiene-b-styrene) triblock copolymers. SBS (scSBS) 65
Sulfonated poly(ether ether ketone). SPEEK 66
Sulfonated poly(ether ether ketone) and crosslinked. SPEEK-C 67
Aromatic Poly(ether ketone)s with Pendant Sulfonic Acid Phenyl. Me-SPEEKDK& Ph-SPEEKDK 68

(Continues)

1216 Int. J. Energy Res. 2011; 35:1213–1228 # 2011 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Methanol crossover in direct methanol fuel cells M. Ahmed and I. Dincer

Table I. (Continued)

PEM Abbreviations Reference

Polymerized polypyrrole on sulfonated poly(arylene ether ketone). SPAEK-C-(PPY/PWA)n 69

Sulfonated poly(arylene ether sulfone) copolymer. BPSH 70
Cross-linked sulfonated poly (arylene ether ketone). SPAEK-C/PVA 71
polyaniline on sulfonated poly(arylene etherketone) SPAEK-C (PANI/PWA)n 72
Cross-linked sulfonated poly(arylene ether ketone). C-SPAEK 73
Sulfonated plasma polymerized. SPPM 74
Zwitterionic crosslinked proton exchange. NaSS-4VP 75
Sulfonated poly(styrene). SPS 76
Sulfonated poly(arylene ether ether ketone ketone) copolymers. SPAEEKK 77
Sulfopropylated ethylene-vinyl alcohol copolymers. s-EVOHs 78
Blend Membranes
Partially sulfonated polymer blend. sPS/sPPO 79
Poly(vinyl alcohol) and its ionic blends with sodium alginate and chitosan. PVA/SA/CS 80
Poly(ether ether ketone)/Polyvinyl alcohol blend. SPEEK/PVA 81
A polyvinyl alcohol/p-sulfonate phenolic resin PVA/SP 82
Crosslinked poly(vinyl alcohol) containing sulfosuccinic acid. PVA/SSA 83
Novel covalent-ionically cross-linked. C-SPEEK 84
Polyelectrolyte complex (PEC). CS/(P(AA-AMPS) 85
Poly(2,6-dimethyl-1,4-phenylene oxide)-based acid–base polymer blend. PPO 86
Blends of ethylene-propylene-diene terpolymer (EPDM) and organophilized silicas. EPDM 87
Composite Membranes
Crosslinked sulfonated poly(ether ether-ketone) /silica hybrid. SPEEK/SiO2 88
Poly(vinyl alcohol) sulfosuccinic acid silica hybrid. PVA/SiO2 89
Poly(vinyl alcohol) with embedded phosphotungstic acid. PVA/PWA 90
Chitosan/titanate Nanotube Hybrid. CS/TNT 91
a-zirconium phosphate and silicotungstic acid. PVA/ZrP/SWA 92
Inorganic–organic hybrid–poly siloxane/poly (mal eicimide-co-styrene) network. AESA-Na 93
Poly(vinyl alcohol)/sulfated b-cyclodextrin. PVA/sulfated -cyclodextrin 94
Zeolite beta-filled chitosan. CS/Beta/SO3H 95
Poly(vinyl alcohol) with polyimide/ 8-trime thoxy- silyl pro pyl glycerine ether-1, PI-PVA-TSGEPS 96
3,6-pyrenetrisulfonic acid composite.
Organic-inorganic hybrid alkaline by epoxide ring. AEMs s 97
Polyvinyl alcohol pervaporation. PVA 98
Sulfonated poly(styrene-ran-ethylene) and porous polyimide matrix. PI/SPES 99
Self-cross-linkable sulfonated poly(ether ether ketone). SPEEK 100
Phosphorylated titanate nanotubes embedded nanocomposite. CS/PTNT 101
Solid superacid embedded chitosan hybrid. CS/STiO2 102
Organic–inorganic hybrid. CS/silica 103
Sulfonated poly(ether ether ketone) /tung stopho sphoric acid/ mesoporous SPEEK/TPA/MCM-41 104
materialcomposite.
sulfonated mesoporous benzene-silica incorporated poly(ether ether ketone) sPEEK-OMB 105
composite.
Poly(vinyl alcohol)-based hybrid Nanocomposite. PVA/SSA/sPBS 106
Sulfonated poly(ether ether ketone) sub-layer and polyvinyl alcohol sub-layer. SPEEK/ PVA 107
Functionalized carbon nanotube-poly(arylene sulfone) composite. PtRu/CNT-sPAS 108
Sulfonated polystyrene/polytetrafluoroethylene composite. SPS/PTFE 109
Dodecylbenzene sulfonic acid-doped/ polyethylene glycol/SiO hybrid. DBSA-PEG / SiO2 110
Chitosan-Poly (Vinyl Alcohol) and Calcium Oxide Composite. CPV 111
Macroporous polyimide composite. PAMPS 112
A cross-linked hybrid. SPAEK 113
Sulfonated and hydrogenated styrene/butadiene blocks copolymer PE-SHSBS 114
and plasma-treated microporous polyethylene.
Benzimidazole grafted poly(ether ether ketone and sulfonated poly(ether SPEEK-PEEK-BI 115
ether ketone) composite.
SPEEK/PVDF/PWA 116

(Continues)

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DOI: 10.1002/er
M. Ahmed and I. Dincer
Table I. (Continued)
PEM
Sulfonated poly(ether ether ketone), poly(vinylidene fluoride) and
phosphotungstic acid.
Nitrated sulfonated poly(ether ether ketone).
Sulphonated tetramethyl poly(ether ether ketone)/epoxy/sulphonated
phenol novolac semi-IPN.
*polymer
PEM, polymer-electrolyte membrane.
sulfosuccinic acid [83], and crosslinked (sulfonated poly
ether ether ketone) [84].
Composite membranes. A number of composite mem-
branes have been synthesized to reduce methanol crossover
and improve proton conductivity for DMFCs such as inor-
ganic–organic material [88–97], composite with organic
[98–100], composite with inorganic [101–104], nanocom-
posite [105,106], and multilayer composite [107].
4. 2. Transport properties of membranes
An electrolyte with high proton conductivity and low
methanol crossover is the key element of direct methanol
fuel cells. To gain understanding of the methanol crossover
process in PEMs, transport phenomena in membranes must
be considered. Therefore, in this section transport proper-
ties related to methanol crossover such as transport of pro-
ton (proton conductivity) and transport of methanol
(methanol permeability) are discussed. As previously
reported, the reviewed membranes are classified into four
categories such as modified Nafion membranes, copolymer
membranes, blend membranes, and composite membranes.
4. 2. 1. Modified Nafion membranes
Figure 2(a). shows the results of proton conductivity and
methanol permeability of modified Nafion membranes for
DMFCs as listed in Table I. The most favorably industrial re-
gion lies to the top left of Figure 2(a) (i.e., high proton conduc-
tivity and low methanol permeability). Based on the figure,
a significant achievement was observed in both proton con-
ductivity and methanol permeability. The proton conductivity
improved from 0.0032Scm-1 (point #1) for Pd nanophases
in a Nafion polymer [28] to 0.117Scm-1 (point #30) for
Nafion/porous layered oxide nanocomposite [33], that is,
increasing by about 36 times, which is remarkably higher
than that of 0.026Scm-1 for Nafion 117. In addition, the meth-
anol permeability decreases from 7.2610-6 cm2 s-1 (point #7)
for Nafion/nano-size sulfated titanium dioxide solid
superacid composite [25] to 0.021710-6 cm2 s-1 (point #2)
for organic–inorganic hybrid-laminated Nafion 115 [18],
that is, decreasing by about 333 times. A work on Nafion/Zirco-
nium meta-sulfonphenyl phosphonic acid-incorporated com-
posite membrane with different concentration percentage of
1218
Methanol crossover in direct methanol fuel cells
Abbreviations Reference
Nitrated SPEEK 117
STMPEEK/TMBP/PNBS 118
zirconium meta-sulfonphenyl phosphonic acid (Zr-msPPA)
[38], and Nafion-infiltrated composite membrane [29]
reports conductivities of the same order of magnitude as
Nafion 117 and significant reduction of methanol perme-
ability. These works are shown as (points #17, and #27)
in Figure 2(a). The reduction in methanol permeability is
attributed to the nano crystalline layer-developed
interior of the Nafion 117 membrane [38]. The preceding
discussion highlights the range of transport properties of
modified Nafion membranes reported in previous literatures.
Figure 2(b) shows the variation of selectivity versus
proton conductivity of modified Nafion membranes for
DMFCs as listed in Table I. The most favorably industrial
region lies to the top right of Figure 2(b) (i.e., high proton
conductivity and selectivity). The selectivity parameter
determines the ratio of proton conductivity to methanol
permeability of a membrane and the higher selectivity
value leads to a better membrane performance. Based on
the figure, the maximum selectivity value of 170104
Sscm3 was achieved by both Nafion/zirconium meta-
sulfonphenyl phosphonic acid-incorporated [38], and
Nafion-infiltrated composite membranes [29] which is sig-
nificantly (43 folds) higher than that of 4.0104 Sscm-3 for
Nafion117. It is followed by Nafion/2-acrylamido-2-
methylpropanesulfonic acid-modified mont-morillonite
membrane (AMPS-MMT/N) [26]. It was found that selec-
tivity value of about 90104 Sscm-3 is achieved at 3.0wt.%
of AMPS-MMT. In fact, such a remarkably improved se-
lectivity parameter of Nafion matrices is owing to the ef-
fective role of AMPS-modified nanolayers in restricting
methanol permeation while maintaining essential proton
conduction properties.
4. 2. 2. Copolymer membranes
Figure 3(a) shows the results of proton conductivity and
methanol permeability of copolymer membranes for
DMFCs as documented in Table I. Based on the figure, a
significant achievement was observed in both proton con-
ductivity and methanol permeability for different copolymer
membranes. It was found that the proton conductivity
improved from 0.00025Scm-1 (point #4) for sulfonated
polyethersulfone Cardo [62] to 0.181Scm-1 (point #13)
for sulfonated plasma polymerized [74], that is, increasing
by about 724 times, which is significantly higher than that
of 0.026Scm-1 for Nafion117. In addition, the methanol
Int. J. Energy Res. 2011; 35:1213–1228 # 2011 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Methanol crossover in direct methanol fuel cells
Figure 2. (a) Variations of the measured proton conductivity ver-
sus methanol permeability for modified Nafion membranes. (b)
Variation of selectivity (conductivity/permeability) versus proton
conductivity for modified Nafion membranes from the litera-
tures: ( ) Pd/Nafion [17], ( ) Nafion115/Hy [18], ( ) Nafion/
P [19], ( ) Nafion117-Pd [23], ( ) Nafion/sDDS [27], ( ) N/
MPMDMS [24], ( ) TiO2/SO4 2[25], (X) SiO2/N [28], (+) sPFR/
Nafion [20], () Nafion/silica [34], ( ) Nafion/PPO-PMA [39],
( ) Nafion/AMPS [21], ( ) Nafion/clay [35], ( ) N/SPEEK
[41], ( ) TEOS/DEDMS [42], ( ) HTN [43], ( ) PI/Nafion [29],
(*) N/SILCPM [46], (^) Nafion/AFB [30], (&) Nafion [22], ( )
Nafion/TiO2 [31], ( ) Nafion/sb-CD [44], ( ) AMPS/MMT/N
[26], ( ) PDDA/PM/Nafion [40], ( ) STP/Nafion [37], ( )
Fe2O3/SO24/Nafion [32], ( ) Zr-msPPA/Nafion [38], (#) Nafion /
PA/PY[47], ($) N/SPEEK [45], (C) N/APO [33], (@) N115/PI–PVA–
TSPS [36].
permeability decreases from 6.4610-6 cm2 s-1 (point #19)
for zwitterionic crosslinked proton exchange [75] to
0.000810-6 cm2 s-1 (point #3) for sulfonated polyimides
[52], that is, decreasing by about 8100 times. A work on
polyaniline on sulfonated poly(arylene ether ketone) with
Int. J. Energy Res. 2011; 35:1213–1228 # 2011 John Wiley & Sons, Ltd.
DOI: 10.1002/er
M. Ahmed and I. Dincer
Figure 3. (a) Variations of the measured proton conductivity ver-
sus methanol permeability for copolymer membranes. (b)
Variation of selectivity (conductivity/permeability) versus proton
conductivity for copolymer membranes from the literatures:
( ) SSEBS [48], ( ) Co-SPIs [51], ( ) SPI [52], ( ) SPES-C
[62], ( ) S-SIBS [63], ( ) SPS [76], ( ) SEBS [49], ( ) BAPS/
ODA [53], ( ) 6FCN-35/BPSH-40 [50], ( ) NTDA/DAPPS/ODA
[64], ( ) SPAEEKK [77], ( ) SPAEK-C-(PPY/PWA)n [69], ( )
SPPM [74], ( ) SBS (scSBS) [65], ( ) SPEEK [66], ( ) BPSH
[70], ( ) SPPES [54], ( ) SPEEK-C [67], ( ) NaSS-4VP [75],
( ) SPES-C [55], ( ) SPI-K [56], (a) SPAEKs [57], (C) SPAEK-C/
PVA [71], (@) SPAEK-C (PANI/PWA)n [72], (#) Cr-SPAEK [58],
($) C-SPAEK [73], (+)s-EVOHs [78], (*) S-PAES [59], (&)Me-
SPEEKDK & Ph-SPEEKDK [68], (^)C-ABPS H40 [60], (X)
C-SPAEK [61].
thin polyaniline (PANI) and phosphotungstic acid (PWA)
multilayers coated [72], Polymerized polypyrrole on sulfo-
nated poly(arylene ether ketone) by deposit polypyrrole
(PPY) and phosphotungstic acid (PWA) layer by layer
[69], and Sulfonated Poly(arylene ether ether ketone ketone)
1219
M. Ahmed and I. Dincer Methanol crossover in direct methanol fuel cells

copolymers with phthalazinone [77] reports conductivities

of the same order of magnitude as Nafion and a significant
reduction of methanol permeability. These works are
shown as (points #24, #12, and #11) in Figure 3(a). The re-
duction in methanol permeability is attributed to the thin
polyaniline, and phosphotungstic acid multilayers coated
[72], and deposit polypyrrole and phosphotungstic acid
layer by layer [69]. The above discussion presents the
available range of transport properties of copolymer mem-
branes reported in previous literatures.
Figure 3(b) shows the variation of selectivity versus
proton conductivity of copolymer membranes for DMFCs
as listed in Table I. Based on the figure, several copolymer
membranes achieved higher values of selectivity, the max-
imum selectivity value of 311104 Sscm3 was achieved
by Sulfonated polyimides with sulfonation level 16mol %
(SPI). However, the proton conductivity is one order of mag-
nitude less than that of Nafion 117 [52]. It is followed by
Polymerized polypyrrole on sulfonated poly (arylene ether
ketone) [69] with selectivity of 247104 Sscm3, and sul-
fonated plasma polymerized [74] with selectivity of 243
104 Sscm3. In addition, it was found that selectivity value
of about 202104 Sscm3 is achieved by polyaniline on
sulfonated poly(arylene ether ketone) [72].

4. 2. 3. Blends membranes
Figure 4(a). shows the results of proton conductivity
and methanol permeability of blends and composite blends
membranes for DMFCs as listed in Table I. Based on the
figure, a significant achievement was observed in both pro-
ton conductivity and methanol permeability. The proton
conductivity improved from 0.002Scm-1 (point#7) for
poly(ether ether ketone)/polyvinyl alcohol blend [81] to
0.11Scm-1 (point #1) for crosslinked poly(vinyl alcohol)
containing sulfosuccinic acid [83], that is, increasing by
about 55 times, which is remarkably higher than that of
0.026Scm-1 for Nafion117. In addition, the methanol per-
meability decreases from 11.7810-6 cm2s-1 (point # 7)
for poly(ether ether ketone)/polyvinyl alcohol blend [81]
to 0.05810-6 cm2s-1 (point # 6) for Novel covalent-
ionically cross-linked [84], that is, decreasing by about
203 times. A work on Poly(2,6-dimethyl-1,4-phenylene
oxide)-based acid–base polymer blend [86], and polyelec-
trolyte complex (PEC) [85], reports conductivities of the
same order of magnitude as Nafion and a significant reduc-
tion of methanol permeability. These works are shown as
(points #5, and #4) in Figure 3(a). The reduction in meth-
anol crossover is attributed to the solution of
bromomethylated-poly (2,6-dimethyl-1,4-phenylene oxide)
(BrPPO) [86]. The above reported discussion emphasizes
the range of transport properties of modified Nafion mem-
branes reported in previous literatures.
Figure 4(b). shows the variation of selectivity versus
proton conductivity of blends and composite blends mem-
branes for DMFCs as listed in Table I. The selectivity pa-
rameter determines the ratio of proton conductivity to
methanol permeability of a membrane and the higher selec-
tivity value leads to a better membrane performance. Based
Figure 4. (a) Variations of the measured proton conductivity ver-
sus methanol permeability for blends membranes. (b) Variation
of selectivity (conductivity/permeability) versus proton conduc-
tivity for blends membranes from the literatures: ( ) PVA/SSA
[83], ( ) sPS/sPPO [79], ( ) PVA/SA/CS [80], ( ) CS/(P(AA-
AMPS) [85], ( ) PPO [86], ( ) C-SPEEK [84], ( ) SPEEK/PVA
[81], ( ) EPDM [87], ( ) PVA/SP [82].
on the figure, the maximum selectivity value of 81104
Sscm3 was achieved by Poly (2,6-dimethyl-1,4-pheny-
lene oxide)-based acid–base polymer blend [86], which is
significantly higher than that of 4104 Sscm3 for
Nafion117. In fact, such a remarkably improved selectivity
parameter is owing to the effective role of (BrPPO) in
restricting methanol permeation while maintaining essen-
tial proton conduction properties.
4. 2. 4. Composite membranes
Figure 5(a) shows the results of proton conductivity and
methanol permeability of composite membranes for
DMFCs as reported in Table I. Based on the figure, a sig-
nificant achievement was noticed in both proton conductiv-
ity and methanol permeability. The proton conductivity

1220 Int. J. Energy Res. 2011; 35:1213–1228 # 2011 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Methanol crossover in direct methanol fuel cells
Figure 5. (a) Variations of the measured proton conductivity ver-
sus methanol permeability for composite membranes. (b) Varia-
tion of selectivity (conductivity/permeability) versus proton
conductivity for composite membranes from the literatures:
( ) SPEEK/SiO2 [88], ( ) PVA/SiO2 [89], ( ) CS/(P(AA-AMPS)
[108], ( ) SPS/PTFE [109], ( ) DBSA-PEG / SiO2 [110], ( )
PVA/PWA[90], ( ) PVA [98], (X) CS/PTNT [101], ( ) CS/STiO2
[102], ( ) CS/silica [103], ( ) PI/SPES [99],( ) CS/TNT [91],
( ) sPEEK-OMB [105], ( ) PVA/SSA/sPBS [106], ( ) SPEEK/
PVA [107], (+) CPV [111], () SPEEK/TPA/MCM-41[104], () PAMPS
[112], () PVA/ZrP/SWA [92], ( ) AESA-Na [93],( ) SPEEK [100],
( ) SPAEK [113], (@) PVA/sulfated b-cyclodextrin [94] ($) PE-
SHSBS [114], (a) SPEEK-PEEK-BI [115],(C) SPEEK/PVDF/PWA
[116],(#) CS/Beta/SO3H [95], (&) Nitrated SPEEK [117], (^)
STMPEEK/TMBP/PNBS [118], (*) PI-PVA-TSGEPS [110], ()
AEMss [97].
improved from 0.00013Scm-1 (point #7) for polyvinyl
alcohol pervaporation [98] to 0.25Scm-1 (point #19) for
macroporous polyimide composite [112], that is, increas-
ing by about 1920 times, which is significantly higher than
that of 0.026 Scm-1 for Nafion117. In addition, the metha-
nol permeability decreases from 1210-6 cm2s-1 (point # 15)
Int. J. Energy Res. 2011; 35:1213–1228 # 2011 John Wiley & Sons, Ltd.
DOI: 10.1002/er
M. Ahmed and I. Dincer
for sulfonated poly (ether ether ketone) sub-layer and poly-
vinyl alcohol sub-layer [107] to 0.00910-6 cm2s-1 (point
#7) for Polyvinyl alcohol pervaporation [98], that is, de-
creasing by about 1333 times. A work on Sulfonated poly-
styrene/polytetrafluoroethylene composite (SPS/PTFE)
[109], Sulfonated poly(styrene-ran-ethylene) and porous
polyimide matrix (PI/SPES) [99], and Sulfonated and hy-
drogenated styrene/butadiene block copolymer and
plasma-treated microporous (PE-SHSBS) [114] reports
conductivities of the same order of magnitude as Nafion
and a significant reduction of methanol permeability.
These works are shown as (points #4, points #11, and
#24) in Figure 5(a). The reduction in methanol permeabil-
ity in (SPS/PTFE) is due to increasing DVB (a crosslinker)
content. Increasing crosslinking density results in the in-
crease of the diffusion resistance of methanol over water,
finally, resulting in the suppression of methanol perme-
ation or methanol crossover [109].
Figure 5(b) shows the variation of selectivity versus
proton conductivity of composite membranes for DMFCs
as listed in Table I. The selectivity parameter determines
the ratio of proton conductivity to methanol permeability
of a membrane. Based on the figure, the maximum selec-
tivity value of 73104 Sscm3 was achieved by sulfonated
poly(styrene-ran-ethylene) and porous polyimide matrix
[99], which is significantly higher than that of 4104
Sscm3 for Nafion 117. It is followed by sulfonated
polystyrene/polytetrafluoroethylene composite membrane
[109], where the selectivity value is about 62104
Sscm3. On the other hand, the ratio of styrene/divinylben-
zene (styrene/DVB) of 85/15 attains the lowest methanol
permeability. In fact, such a remarkably improved of selec-
tivity parameter is due to the sharp decrease in methanol
permeability with increasing crosslinking density. It was
found that crosslinking is restricting methanol permeation
while maintaining essential proton conduction properties
[109].
To conclude based on the above discussion, there is a
significant potential for the development of membrane
architectures that can allow more independent control over
the proton conductivity, and methanol permeability charac-
teristics. Consequently, achieving of highly selective
PEMs is very encouraging because PEMs with greater se-
lectivity have potential for improved DMFC performance.
It is worth mentioning that just because selectivity of a
PEM is higher than Nafion, does not mean improved
DMFC performance can be achieved. One limitation of se-
lectivity as a gauge of DMFC performance is due to the
fact that a minimum conductivity is still required for
DMFC operation, regardless of how low methanol perme-
ability is.
4.3. Membrane thickness
It was reported that the thickness of the Nafion membrane
is one of the most essential factors in determining the
methanol crossover rate. The methanol crossover decreases
with the increase of thickness, whereas increasing the
1221
M. Ahmed and I. Dincer
thickness reduces the power density because of it high
ohmic loss [119]. However, this trend changes at the highest
current densities because membrane resistance to transport
phenomena became dominant. This fact is related to the re-
duction of resistance of charge transfer from the anode side
to the cathode side, and the reduction of concentration polar-
ization in the polymer with the decreasing of membrane
thickness. Thus, the electrical performance of fuel cell with
membranes of various thicknesses shows that the perfor-
mance trend is probably determined by the combined effects
of proton conductivity and fuel crossover. Something similar
occurs with the influence of the equivalent weight in the
performance of the cell. But at highest density currents, the
electrical performance of a DMFC may be decrease when
the equivalent weight of the membrane decreases [120].
It was found for composite Nafion-based membranes
that both the conductance and the methanol permeation
rate show a significant decrease with increasing thickness.
The optimization of these parameters regarding favorable
properties is difficult. Moreover, for thinner membranes,
the permeation rate changes by a factor of four to five with
a temperature change from 25 to 65
C, whereas in the
thicker membranes this factor is about three. At lower
temperatures, the variation of the methanol flux through
the membranes versus thickness is small compared with
that at 65
C. Also, a strong decrease of permeation with
thickness is observed [121]. It was found that the methanol
crossover limiting currents significantly decreases with the
membrane thickness for disulfonated polyarylene ether
benzonitrile copolymers and Nafion at 80
C [122].
4.4. Methanol concentration
In fact, a higher methanol concentration is desirable in
DMFCs because of higher energy density. Therefore,
many researchers are investigated the influence of metha-
nol concentration on methanol crossover to the cathode
side. Figure 6 shows the variation of methanol permeabil-
ity versus methanol concentration (M) for different types
of membranes as reported in previous literatures. It was
found that the methanol permeability of sulfonated poly
ether ether ketone [123], sulfonated poly ether ether ketone
(SPEEK55) [107], Nafion [22], Nafion 115 [94], and
Nafion117 [95] increases with the increase of methanol
concentration. However, the methanol permeability of sul-
fated poly (vinyl alcohol) decreased as the concentration of
methanol increases. Also, adding sulfated poly (vinyl alco-
hol) to sulfonated poly(ether ether ketone) membranes can
suppress the methanol crossover especially at high metha-
nol concentration [123,107]. The methanol permeability
decreases with increasing methanol concentration of the
acid treated sulfonated montmorillonite / sulfonated poly
(ether ether ketone) nanocomposite membranes [124].
A work on three-dimensionally ordered macroporous
(3DOM) polyimide matrix composite [112] indicated that
the methanol permeability decreased with increasing meth-
anol concentration. It was found that by applying the 3DOM
matrix, the methanol permeability of 2-acrylamido-2-
1222
Methanol crossover in direct methanol fuel cells
Figure 6. Variation of Methanol permeability versus Methanol
concentration (M) for different types of membranes reported in
the literatures: ( ) SPEEK/SPVA [123] ,( ) SMMT/SPEEK
[124], ( ) SPEEK/ PVA [107], ( ) PAMPS[112], ( ) Nafion/
hydroxyapatite composite [125], ( ) CS/Silica [103], ( ) Nafion
[22], ( ) PVA/sulfated b-cyclodextrin [94] ,( ) CS/Beta/SO3H
[95],( ) Nafion 115 [94], ( ) Nafion117 [95], ( ) Co-SPIs
[51], ( ) NTDA–BAPBDS/DABI [126], ( ) PVA/PSSA–MA [127].
methylpropanesulfonic acid polymer (PAMPS) was reduced
because of its effect on the size and distribution of hydro-
philic channels responsible for methanol permeation. Also,
the permeability of Nafion/hydroxylapatite composite mem-
brane [125], and chitosan/silica [103] decrease by the in-
crease of methanol concentration. Work on poly (vinyl
alcohol)/sulfated b-cyclodextrin [94], and chitosan/Beta/
SO3H [95] indicated that a reduction of methanol cross-
over was observed, as methanol concentration increased.
This is attributed to the excellent methanol resistance of
hydroxyls in poly(vinyl alcohol) [94]. The incorporated
zeolite beta particles can extend the diffusion path length
of methanol in the membrane, rigidify the chitosan chains,
and compress the volumes among chitosan chains. These
reasons caused the decrease in methanol crossover of
chitosan/Beta hybrid membranes [95].
A work on 1,4,5,8-naphthalenetetracarboxylic dianhy-
dride (NTDA), based sulfonated polyimides (SPIs) [126]
shows the methanol permeability decreases with increasing
methanol concentration. Also, the methanol permeability
of poly(vinyl alcohol)/poly(styrene sulfonic acid-co-maleic
acid) (PVA/PSSA–MA) membrane [127] is at least seven
times lower than those of Nafion 117 in all methanol
concentration ranges. In addition, the increase of methanol
concentration leads to a slight decrease of methanol perme-
ability through PVA/PSSA–MA membrane. On the other
hand, in the work on sulfonated co-polyimides (co-SPIs),
the methanol permeability is hardly depended on methanol
concentration [51].
In summary, the methanol permeability increases with in-
creasing the methanol concentration for SPEEK [123], and
Int. J. Energy Res. 2011; 35:1213–1228 # 2011 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Methanol crossover in direct methanol fuel cells
Nafion [22,94,95] membranes. However, a significant
decrease in methanol crossover was reported by increasing
the methanol concentration for SPEEK/SPVA [123],
SMMT/SPEEK [124], SPEEK/ PVA [107], PAMPS
[112], Nafion/ hydroxyapatite composite membrane
[125], CS/Silica [103], PVA/sulfated b-cyclodextrin [94],
CS/Beta/SO3H [95], NTDA–BAPBDS/DABI [126], and
PVA/PSSA–MA [127]. No significant change of methanol
permeability by increasing methanol concentration for
Co-SPIs [51] was observed.
Figure 7 shows the variation of methanol crossover
limiting current density (mAcm-2) versus methanol con-
centration (M) for different types of membranes. For the
Pd/Nafion 117 membranes, the methanol crossover limit-
ing current results at 20
C (point # 1), and 60
C (point
#2) with 1, 2, and 5M methanol solution are shown in
the figure . It was found that methanol crossover increased
with the increase of methanol concentration because of
higher concentration gradient. In addition, the value of
methanol crossover limiting current density increased with
increasing cell temperature. This is caused by a severe
membrane swelling with the higher temperature methanol
solution. It was noticed that methanol crossover was sup-
pressed by incorporating of Pd into the membrane, and
lower crossover was seen with a higher Pd loading mem-
brane [128]. More importantly, the methanol crossover of
Nafion 117 membrane with 1 and 5M methanol was signif-
icantly reduced by impregnating Pd.
A work on a pore-filling (PF) polymer electrolyte mem-
brane (point # 3) shows that the methanol crossover
through Nafion117 membrane increased with methanol
concentration, whereas methanol crossover through PF
membrane saturated at high methanol concentration. This
Figure 7. Variation of Methanol crossover current versus Meth-
anol concentration (M) for different types of membranes
reported in the literatures: ( – ) Pd/Nafion [128], ( ) pore-
filling membranes [129], ( ) Pd-Cu[130], ( ) Nafion [131],
( – ) Nafion/Silica Hybrid [132], ( - ) PBI/PVPA [133].
Int. J. Energy Res. 2011; 35:1213–1228 # 2011 John Wiley & Sons, Ltd.
DOI: 10.1002/er
M. Ahmed and I. Dincer
is because the swelling of the filling polymer electrolyte
of the PF membrane was prevented, and the solvent con-
tent of the PF membrane was kept lower than that of
Nafion117 membrane [129]. A work on Pd and Pd–Cu
alloy deposited Nafion membranes indicated that the
methanol crossover current is significantly greater for
unmodified membrane (point #4), and increases with in-
creasing methanol concentration. The difference in
methanol crossover current density is more pronounced
between the Pd-sputtered and bare Nafion membranes
with increasing concentration. This is indicating the
effective suppression of methanol crossover by the Pd-
sputtered membrane for higher methanol concentrations.
The possible mechanism leading to the lower methanol
crossover rate in the Pd and Pd–Cu alloy sputtered
membranes is attributed to the effect of the coated Pd
or Pd–Cu alloy, which is physically blocked by the pas-
sage of methanol molecules [130].
For Nafion 112 and 1135 membranes (point #5) at
60
C, the crossover current density is approximately line-
arly proportional to the methanol concentration, with the
Nafion 112 membrane featuring higher crossover rate.
The difference in crossover current density between the
two membranes diminishes with methanol concentration;
for example, the difference decreases from 32mAcm-2 at
2M to11mAcm-2 at 4M. Thicker membranes have higher
cell internal resistance but lower methanol crossover.
Therefore, the cell using Nafion 1135 has the best electro-
chemical performance, and its power density is insensitive
to the anode stoichiometry [131].
The methanol crossover currents density at 25
C (point
#6), and 80
C (point #7), measured with Nafion/silica
hybrid membranes as a function of methanol concentra-
tion are shown in the figure. It was found that the methanol
crossover current increases with increasing methanol con-
centration [132]. The methanol crossover rate for celtec-V
was measured at different methanol feed concentrations
and cell temperatures at 60
C (point #8), and 90
C (point
#9). Methanol permeation increases in an approximately
linear correlation with the methanol concentration. Also,
methanol crossover increases with the increase of the
temperature. This is of utmost importance from a perfor-
mance point of view. Furthermore, a lower crossover rate
is associated with higher fuel efficiency for the same con-
centration or a gain in volumetric energy density of the
fuel. Comparing the methanol crossover with Nafion,
Nafion shows significantly large values [133].
The relationship between limiting current density and
methanol concentration can be estimated from the
 
following equation JI ¼ 6FD L Cin . Where JI is a steady
state limiting current density; Cin is the methanol concen-
tration at the feed edge. This equation was developed by
assuming that the methanol crossover is only because of
diffusion [10]. Based on the above equation, the variation
of limiting current density is linearly increased with the
methanol concentration, if the diffusion coefficient is con-
stant. However, increasing the temperature leads to an
1223
M. Ahmed and I. Dincer
increase of diffusion coefficient. This will result in increasing
the limiting current density as the temperature increases.
4.5. Fuel cell temperature
Figure 8 shows the methanol permeability as a function of
temperature for different types of membranes reported in
the literatures: Nafion 117 and Phosphonated polypho-
sphazene [134], sulfonated poly(arylene ether sulfone) co-
polymer (BPSH) [70], sulfonated polyethersulfone Cardo
(SPES-C) [62], Sulfonated poly(ether ether ketone)
(SPEEK) [66], sulfonated poly(styrene) (SPS) [76], sulfo-
nated poly(styrene-isobutylene-styrene) (S-SIBS) [63],
sulfonated co-polyimide (Co-SPIs) [51], Nafion112 [51],
partially fluorinated ionomeric [135], sulfonated poly(ary-
lene ether sulfone)–silica nanocomposite [136], sulfonated
poly(phthalazinone ether sulfone) (SPPES) [54], and sulfo-
nated poly(ether ether ketone)/poly(vinylidene fluoride)/
phosphotungstic acid (SPEEK/PVDF/PWA) [116]. Based
on the figure, the methanol permeability of all membranes
increases with the increase of temperature. In addition, an
Arrhenius-type dependency of methanol permeability on
temperature exists for all these membranes. It is worth not-
ing that the methanol permeability of the SPES-C [62],
SPS[76], S-SIBS[63], membranes are considerably smaller
than that of both Nafion 117, and Nafion 112 membrane
over the temperature range measured. We also observed
the similar results of methanol permeability in SPEEK
[66], SPPES [54], and SPEEK/PVDF/PWA membranes
[116]. It is important to note that the methanol permeability
of these membranes is considerably smaller than that of
Figure 8. Variation of methanol permeability versus cell temper-
ature for different types of membranes reported in the litera-
tures: ( ) Nafion 117 [134] ,( ) Phosphonated
polyphosphazene [134], ( ) BPSH [70], ( ) SPES-C [62],
( ) SPEEK [66], ( ) SPS [76], ( ) S-SIBS [63], ( ) Co-SPIs
[51], ( ) Nafion 112 [51], ( ) Partially Fluorinated Ionomeric
[135], ( ) Sulfonated oly(arylene ether sulfone)–silica nanocom-
posite [136], ( ) SPPES[54], ( ) SPEEK/PVDF/PWA [116].
1224
Methanol crossover in direct methanol fuel cells
Nafion 117, and Nafion 112 membranes over the tempera-
ture range 25–80
C. The different methanol permeation of
these membranes and Nafion membranes can be explained
by the difference in their microstructures.
To conclude, the methanol permeability increases with
the increase of temperature, and an Arrhenius-type depen-
dency of methanol permeability on temperature exists for
all these membranes. The methanol permeability of SPES-
C, SPS, S-SIBS, SPEEK, SPPES, and SPEEK/ PVDF /
PWA is much less than that of Nafion.
5. ACHIEVEMENTS
Although great improvements in fuel cell design and com-
ponents have been made over the past years, several issues
remain to be addressed before PEM fuel cells can become
competitive enough to be used commercially. Polymer-
electrolyte membranes in DMFC should transport protons
as an electrolyte and prevent the methanol crossover. To
reduce methanol crossover, different approaches are fol-
lowed. The most important approaches considered in this
manuscript are (1) to modify the Nafion membrane, (2) to
develop alternative membranes, or (3) exploring composite
polymer materials.
1. A work on modified Nafion membranes such as Zir-
conium meta-sulfonphenyl phosphonic acid (Zr-
msPPA)/Nafion composite membranes showed a
considerable reduction of methanol permeability
with increasing Zr-msPPA content. This is because
of the Zr-msPPA nano conductors acted as crystal-
line barriers to methanol permeation [137]. However,
the proton conductivity also decreased with increas-
ing Zr-msPPA content, but its effect was not as con-
siderable as with methanol permeation because of the
inherent, high conductivity of Zr-msPPA. The meth-
anol permeability reduced by two orders of magni-
tude (48 times) compared with that of Nafion117,
whereas the proton conductivity is at the same order
of magnitude as Nafion117 [38]. Moreover, the poly-
imide/Nafion (PI/Nafion) composite membrane has a
very low methanol crossover compared with a
Nafion 112 membrane because of the fact that the
composite membrane mechanically prevents Nafion
from swelling and consequently reducing the metha-
nol crossover. The methanol permeability is eighty
times lower than that of Nafion 112. In addition,
the proton conductivity is the same as Nafion 112.
It was reported that there is a significant improve of
the performance of a DMFC with PI/Nafion compos-
ite membrane because of the use of a very thin mem-
brane and a high methanol concentration [97].
2. A work on alternative membranes such as polymer-
ized polypyrrole on sulfonated poly (arylene ether
ketone) SPAEK-C-(PPY/PWA)n [20] shows a con-
siderable decrease of methanol permeability with in-
creasing the number of bilayers compared with the
Int. J. Energy Res. 2011; 35:1213–1228 # 2011 John Wiley & Sons, Ltd.
DOI: 10.1002/er
Methanol crossover in direct methanol fuel cells M. Ahmed and I. Dincer

Nafion 117. It is reported that the SPAEK-C mem- Table II. Transport properties and selectivity of the modified
branes having two regions hydrophilic one, and hy- polymer-electrolyte membranes for direct methanol fuel cells.
drophobic one. Methanol diffuses primarily through PEM Relative Relative Relative Reference
the hydrophilic water-rich regions. When the surface conductivity permeability selectivity #
of SPAEK-C is coated by the polypyrrole (PPY) and
phosphotungstic acid (PWA) films, the electrostatic (Zr-msPPA)/ 0.984–0.45 0.08–0.02 12.3–22.5 38
interactions between the polyacid/poly base pairs Nafion
block the methanol transport pathways [20]. However, (PI/Nafion)* 0.95 0.012 78 97
increasing the number of bilayers of (PPY/PWA) SPAEK-C- 0.91–0.24 0.0313– 28.8–32.6 69
shows a slightly negative effect on proton conductiv- (PPY/PWA)2–10 0.0073
SPPM 1.17 0.0358 32.5 74
ity. The methanol permeability reduced by three
SPAEK-C- 1.224 0.046 26.6 72
orders of magnitude compared with that of Nafion
(PANI/PWA)5
117, whereas, the proton conductivity is the same or-
PI/SPES** 1.47 0.05 29 99
der of magnitude as the Nafion 117. Similarly, a
PPO 0.77 0.047 16.3 86
work on polyaniline on sulfonated poly(arylene ether
ketone) SPAEK-C (PANI/PWA)n[ 72] shows a low *Reference values of Nafion 112.
**Reference values of Nafion 1135.
methanol permeability because of close pores by PEM, polymer-electrolyte membrane.
forming of polyelectrolyte multilayered films on the For the list of the definitions for the aforementioned items, please
substrate surface. The methanol permeability is two refer to Table 1.
orders of magnitude less than that of Nafion 117, and
proton conductivity is higher than that of Nafion 117.

In addition, a work on sulfonated plasma polymerized
(SPPM)[74] shows lower permeability of plasma mem-
branes because of highly crosslinked structure of the
plasma polymerized membranes and their water binding
characteristics, which could effectively restrict methanol
diffusion. The methanol permeability is about 28 times less
than that of Nafion 117, and the proton conductivity is
slightly higher than that of Nafion 117. A work on Sulfo-
nated poly(styrene-ran-ethylene) and porous polyimide
matrix (PI/SPES) composite shows a significant reduction
of methanol permeability because of pore-filling of the
porous PI matrix with SPSE polymer. It results in sup-
pressed water absorption, and less dimensional change
may indicate less methanol crossover though the mem-
brane [99]. A work on poly(2, 6-dimethyl-1,4-phenylene
oxide)-based acid–base polymer blend shows a consider-
able reduction of methanol permeability because of the ef-
fective role of (BrPPO) in restricting methanol permeation
while maintaining essential proton conduction properties.
The methanol permeability is 21 times less than that of
Nafion 117 and the proton conductivity is in the same or-
der of magnitude as Nafion 117 [86].
In summary, the relative transport properties with
respect to Nafion 117 such as conductivity, methanol per-
meability, and selectivity of the best modified membranes
are shown in Table II. The modified Nafion membranes
are (Zr-msPPA)/Nafion, and (PI/Nafion). The developed
alternative membranes are SPAEK-C-(PPY/PWA)n,
SPPM, SPAEK-C-(PANI/PWA)n, PI/SPES, and PPO.
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In this review paper, the development of new PEMs for the
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• The up to date modified membranes with the highest
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PVDF /PWA are much less than that of Nafion.
• The methanol crossover decreases with the increase of
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