Journal of Polymers and the Environment

https://doi.org/10.1007/s10924-017-1146-7

ORIGINAL PAPER

Development of Chitosan Membranes as a Potential PEMFC Electrolyte

Karine N. Lupatini1,2,4 · Jéssica V. Schaffer1 · Bruna Machado1 · Eliane S. Silva1 · Luciana S. N. Ellendersen1 ·
Graciela I. B. Muniz1 · Ricardo J. Ferracin1,3 · Helton J. Alves1,2

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Abstract
Commercial chitosan and chitosan extracted from shrimp shells are being used to design membranes to be tested as low cost
electrolyte in PEM fuel cells. This study investigated the influence of the deacetylation degree (DD) and molar mass (MV) of
the chitosans used in the composition of membranes on its performance regarding to proton conductivity and other properties.
Preliminary results indicate that the chitosan extracted from shrimp shells generated membranes with promising properties
such as proton conductivity, which demonstrated to be even a 100 times higher than those shown by commercial chitosan
membranes. The significant increase in proton conductivity can be associated with the higher number and availability of
amino groups (–NH2) in the chitosan produced in the laboratory, which presents higher DD and lower MV. It is believed that
the properties of chitosan can be manipulated in such a way that it would be possible to obtain proton conductivity values
closer to that presented by Nafion®.

Keywords Proton conductivity · Biopolymers · Hydrogen · Renewable energy · PEMFC

Introduction
Fuel cells (FC) stand out among different emerging technol-
ogies for sustainable energy generation by converting chemi-
cal energy directly into electrical energy [1]. Among the cell
types, the proton exchange membrane fuel cell (PEMFC) has
gained considerable importance due to its great possibility of
applications in mobile. It has also been considered a solution
for rural electrification, which enables the generation and
isolated loads supply in areas where the electrical grid facili-
ties are unviable by the distance from the consumer unit [2].
* Karine N. Lupatini
karinelupatini@gmail.com
1
Laboratory of Catalysis and Biofuel Production
(LabCatProBio), Postgraduate Program in Bioenergy -
Federal University of Paraná (UFPR - Setor Palotina), R.
Pioneiro, 2153, Jardim Dallas, Palotina, PR 85950-000,
Brazil
2
Postgraduation Program in Engineering of Energy
in Agriculture, Western Paraná State University, Cascavel,
PR, Brazil
3
Itaipu Technological Park (PTI), Itaipu Binational,
Foz do Iguacu, PR, Brazil
4
R. Dr. João Gonçalves Padilha, 811, Centro, Pitanga,
PR 85200-000, Brazil
Proton exchange membrane fuel cell are the most efficient
power generation devices, once the electrochemical pro-
cesses involved in PEM are not governed by Carnot Cycle.
Therefore, the efficiency of these cells does not depend
exclusively on the operating temperature of the system. High
efficiency can be achieved at relatively lower temperatures
[3]. The commercial polymer electrolyte membrane cur-
rently used on this type of cell is Nafion® membrane which
presents proton conductivity (σ) of 9.0 × 10−2 S cm−1 at
80 °C [4, 5]. Conductivity of Nafion® is originated from
protons of sulfonic acid groups present at the end of its
chain. Then the water absorbed by the membrane allows the
protons transportation [6].
The most accepted and illustrative theoretical model is
the “cluster network model”, in which sulfonate groups
(SO3−) fixed on the Nafion® structure form ionic clusters
approximately spherical. During the transportation by
structural diffusion or Grotthus mechanism, protons jump
from a hydrated ionic site (SO3− H3O+) to another through
the membrane. It occurs a constant formation and cleavage
of hydrogen bonds between the proton, the water mol-
ecules and the SO3− of the structure. Thus, the proton is
transported migrating through the water cluster structures
in equilibrium towards the cathode, due to the electric field
effect. Whereas in the vehicular transport mechanism, the

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proton is carried by a “vehicle” which leads it from one
point to another within a continuous medium. Considering
proton in an aqueous medium, the transporters are water
molecules that, when diffused carry the protons that are
solvating [7].
Although in the recent years fuel cells (FC) have wide-
spread and emerged as high-efficiency devices in electric
power generation, it still has a high production and mainte-
nance cost, and it also employs materials that originate from
non-renewable sources. In this way, Nafion® becomes a great
example of this conception [4, 5].
It is important to think about actions to reduce the cost
of FC production making it more efficient or sustainable. In
this regard, the use of alternative low cost raw materials in
PEMFC electrolyte production which are able to conduct
protons efficiently at a temperature of 80 °C (temperature
limit for Nafion®) or higher than this has been the subject
of several studies, specially in the obtaining of polymeric
composite materials [5, 8, 9].
A promising alternative is the chitosan, a natural biopol-
ymer predominantly consisting of 2-amino-2-deoxy-D-glu-
cose and 2-acetamido-D-glucose (copolymer), derived from
the N-deacetylation of chitin one of the most abundant poly-
saccharides in nature. It is mainly found in the crustacean
shells, invertebrate skeletal structures, diatom algae and cell
walls of some fungi [10]. About 4.1 million tons/year of
shrimp are produced worldwide generating about 1.2 ton/
year of shells rich in chitin, which are considered an envi-
ronmental liability once it is frequently discarded in landfills
or in other inappropriate ways [11].
Amino (–NH2) and hydroxyl (–OH−) groups present in
chitosan structure facilitates its interaction with other mate-
rials/hydrophilic groups, and thus it is possible to make
structural changes to diversify the possible chemical inter-
actions [9].
In acid medium, chitosan is soluble and becomes a type
of polyelectrolyte positive charge carrier due to the presence
of amino groups which act as a Lewis base, being easily
protonated (–NH3+). In addition, the great availability, low
cost, possibility of structural modification, thermal stability
at temperatures below 150 °C, and easy manufacturing of
thin and resistant membranes make chitosan an interesting
polymeric material to be used as an electrolyte in H2–O2
FC [10, 12].
Physico-chemical properties of the biopolymer mem-
branes can be affected by parameter such as the degree of
deacetylation (DD), the chitosan molar mass (MV) the semi-
crystalline character and the reticulation level resulting from
the conditions employed in the membranes preparation. A
high DD means that a larger quantity of amino groups is
available, and the chains are more extended favoring the
protons conduction. The same phenomena can be observed
with the decrease in crystallinity and MV [13, 14].
13
Journal of Polymers and the Environment
Few studies employ chitosan membranes in protons con-
duction due to the low values demonstrated (σ between 10−7
and 10−3 S cm−1). Accordingly, it is necessary to obtain
composites from the matrices of other polymers, in order
to achieve the most suitable properties for this purpose [5,
8, 9]. Commonly, studies use membranes made from low
DD and high MV commercial chitosan, which serves exclu-
sively as parameters to evaluate the behavior of the compos-
ite biopolymer.
A research conducted by Osifo and Masala [15] aimed
at evaluating the influence of different DD on pure chitosan
membranes with high MV used in direct methanol fuel cell
(DMFC). The authors suggested that chitosan membranes
with high DD must be used in high operating temperatures
of the cell. In the other hand, chitosan with lower DD should
be applied for low operating temperatures, since the result-
ing membranes presented different thermal properties and
flux of protons. However, there are few studies in the litera-
ture that allow a better analysis of the effects and advantages
of using chitosan in obtaining membranes for electrolyte use
in PEMFC.
The aim of the present study was to develop chitosan
membranes extracted from shrimp farming waste to be used
as an electrolyte in PEMFC. It was investigated the influ-
ence of the DD and MV of the biopolymer on its perfor-
mance regarding to the proton conductivity besides other
parameters.
Materials and Methods
Materials
Commercial chitosan with an average molar mass (Sigma-
Aldrich, > 99.8%); hydrochloric acid (Isofar, 36.5–38%);
sodium hydroxide (Synth, 98.0%); glacial acetic acid
(Fmaia, 99.5–100.5%); sodium acetate (Isfar, 99.0%); sul-
furic acid (Synth, 95.0–98.0%); distilled water (1.99 μs).
Commercial Chitosan (CA) and the Chitosan
Produced in the Laboratory (CB)
A sample of commercial chitosan (CA) with an average
molecular mass was used as reference.
Aiming to obtain chitosan in laboratory (CB), first of all
chitin was extracted from freshwater shrimp’s exoskeletons
(shells). It was utilized the species known as Macrobrachium
rosenbergii from a shrimp farming in western Parana State,
in Brazil. The shells were washed in running water, dried in
an electrical oven at 60 °C for 24 h and then milled in a dry
grinding ball mill. It was ground until it is completely sieved
in a 63 µm opening sieve. Obtained materials was subjected
to demineralization and deproteinization according to the
Journal of Polymers and the Environment
method described by Tolaimate et al. [16]. To ensure the
obtaining of a high DD and low MV chitosan, the resulting
chitin was deacetylated in a 50% NaOH solution (m V−1) in
a proportion of 2.5% (m V−1) under reflux for 10 h at 120 °C.
The reaction product was washed in a neutral pH and dried
at 60 °C electric oven for 24 h [13].
A triplicate conductometric titration was performed to
determine the DD percentage of the chitosan samples. It was
used 200 milligrams of biopolymer in 40 mL of 0.05 mol
L−1 hydrochloric acid solution, and it was kept under orbital
shaking for 18 h at 25 ± 0.1 °C. The samples were titrated
in 0.17 mol L−1 sodium hydroxide solution. Thereafter the
Eq. 1 was used for DD determination (%):
16.1 × [base] × (V2 − V1 )
DD = (1)
m madzu diffractometer (Model XRD-6000) in the range of
where V1 is the volume of NaOH (in mL) used for neutral-
izing the excess of HCl, V2 is the volume of NaOH (in mL)
required for neutralization of the protonated chitosan acid
groups (–NH3+), base is the used concentration of NaOH
(in M), and m is the mass of the chitosan sample added to
the acidic solution. V1 and V2 were determined based on
inflections observed in the conductivity graphs (µS cm−1) ×
NaOH (mL) consumed [10].
The average viscosimetric molar mass was obtained by
determining the flow time of the solvent and dilute chitosan
solutions (0.31–0.73 mg mL−1) in 0.3 M HAc/NaAc 0.2 M.
Tests were conducted in triplicate using a Ubbelohde vis-
cometer with a glass capillary (φ = 0.44 mm) immersed in a
thermostated bath with temperature kept at 25 ± 0.1 °C. The
relationship between the intrinsic viscosity [η] (dL g−1) and
the average viscosimetric molar mass of the polymer MV
(Da) was established by Mark–Houwink–Sakurada’s equa-
tion below [17]:
[ ]
̄𝛂
η = KM (2)
V
where K and α are constants for a given polymer–solvent
system which in the case of chitosan varies according to the
DD as well as with the molar mass range [12].
Preparation of Chitosan Membranes MCA and MCB
To obtain each membrane 2.0 g of chitosan were dissolved
in 150 mL of 15% acetic acid (m V−1) in a thermostated
bath at 50 °C. After that it was filtered to remove undis-
solved material, and then the solution was transferred into
a silicone mold and dried in an electric oven at 60 °C for
24 h. The resulting membranes were neutralized in a 0.2 M
NaOH solution for 30 min, washed with distilled water until
it reached neutral pH (7) and then it was stretched for drying
at ambient temperature of 25–30 °C for 24 h [5]. After the
neutralization, some of the membranes were reticulated in
4.0 M sulfuric acid solution for 15 h. The reticulated mem-
branes were neutralized again, washed and dried under the
same conditions mentioned above.
This study evaluated four types of membranes, with avail-
able area of 5 cm × 5 cm, differing from each other with
respect to the chitosan used (CA or CB) and the reticulation
reaction applied. Hence, the tested membranes were termed
as: MCAN (commercial/neutralized); MCAR (commercial/
reticulated); MCBN (laboratory/neutralized); and MCBR
(laboratory/reticulated).
Description of MCA and MCB Chitosan Membranes
X-ray diffraction (XRD) analyzes were conducted on a Shi-
5° < 2θ < 70°, with CuKα radiation (λ = 1.5406 Å; 40 kV;
30 mA) and continuous scanning speed of 1.5° min−1. In
order to improve the results interpretation, the analysis was
also performed on CA and CB powder samples [18].
Infrared spectroscopy (FTIR) the identification of func-
tional groups and their possible displacements were evalu-
ated in the spectral range between 600 and 4000 cm−1 and
resolution of 4 cm−1 in a Vertex 70 spectrophotometer
(Bruker, USA) with attenuated total reflectance (ATR), and
equipped with a carbon crystal at 25 ± 2 °C. The membranes
were placed in a holder and it was compressed at high and
controlled pressure. Each graph produced represents the
result of the average of sixty-four (64) points collected from
the same sample [9].
Water absorption the coefficient of water absorption was
determined by the ratio between the mass of dry and wet
membrane according to Eq. 3, in which ΔM is the coef-
ficient of water absorption, Mw is the mass of the wet mem-
brane, and Md is the mass of the dry membrane. The initial
dry weight was determined by thermal treatment in electric
oven at 60 °C for 24 h. Subsequently, the membranes were
hydrated at temperatures of 40–70 °C for 1 h followed by
excess water removal and weighing the membranes [9].
Mw − Md
ΔM = × 100 (3)
Md
Proton conductivity σ (S cm−1) it was determined by
electrochemical impedance analysis using a testing station
(RSI), described by Paganin et al. [19], and a PGSTAT 30
Autolab potentiostat (Eco Chemie) with associated Fre-
quency Response Analyzer (FRA). The measurements were
performed in open circuit voltage (OCV) with scan rate of
1 mV s−1 in a frequency range of 1.0 MHz–0.1 Hz at the
temperature of 25, 40, 60 and 80 °C, with humidified hydro-
gen gas (prepurified > 99.95%) and oxygen (> 90%). Gas dif-
fusion layer (GDL) was used as electrodes along with a com-
mercial catalyst (Vulcan XC 72) (0.4 mg cm−2 of Pt, 30 wt%
13
 Journal of Polymers and the Environment

Pt/C), and a 0.87 mg cm−2 Nafion®. Membrane resistance

values were determined directly from Nyquist diagrams. The
imaginary component (Z″, y axis) is plotted versus the real
component (Z′, x axis) for each frequency, in which Z′ is the
resistivity of the material (R). The proton conductivity (in S
cm−1), was determined according to Eq. 4:
1 L
σ= . (4)
R A
where L is the distance between the electrodes (cm), A is the
membrane area (cm2) and R is the electric resistance (Ω).

Results and Discussion

DD and MV of the CA and CB Chitosans Fig. 1 MCB membranes in drying process at ambient temperature

According to the conductometric titration curves of the

CA and CB chitosans, the DD calculated from Eq. 1 was
64.3 ± 1.4% for CA and 76.0 ± 0.8% for CB. These results
confirm the efficiency of the chosen method to obtain CB,
once the employed conditions in the deacetylation reaction
provided greater DD than the CA chitosan.
Viscosity measurements were based on solvent flow time
and diluted chitosan solutions. For CA and CB, we adopted
K = 0.074 and α = 0.76, based on obtained DD values [17].
The values of η were determined by the linear slope of the
curve established between samples concentration (g mL−1)
and reduced viscosity (mL g−1) reaching the following val-
ues for CA and CB, respectively: 825.56 and 207.46. There-
fore, MV values for CA and CB were 220.8 and 63.07 kDa,
respectively, indicating that besides CB has a higher DD it
also demonstrates a low MV (more than 3 times lower than in
CA). It is worth pointing out that these results were consist-
ent with the initial aim since larger DD values and smaller Fig. 2 Powder chitosan diffractograms (CA and CB) and chitosan
MV for CB should result in an increase in the number of membranes diffractograms (MCAN, MCAR, MCBN e MCBR)
amino groups available for conducting protons.

Description of the MCA and MCB Chitosan
Membranes
Regarding to appearance, the MCA and MCB chitosan
membranes showed an excellent aspect: transparent and
free of bubbles and particles. Figure 1 shows a picture of
the obtained membranes.
X-ray diffraction (XRD) the main crystalline CA and
CB peaks are located at 2θ = 9.42° and 20° (Fig. 2). The
observed peak at approximately 10° corresponds to the
crystal planes (010), attributed to orthorhombic crystals
derived from α-chitin semi-crystalline structure found in
shrimp shells. The crystalline high intensity peak observed
at about 20° corresponds to planes (110) and (020). Thus,
it can be stated that CB is more amorphous than CA due
to its peak corresponding to plan (010) presents a lower
intensity [10, 13]. In general, it is observed that the dif-
fractograms of chitosan membranes are analogous to each
other and quite different from those of the powder samples.
No clear crystalline peaks were observed for the mem-
branes, only large amorphous halos with main reflections
in two areas of the diffractograms (at 2θ = 19°–21° and
27°–31°). It showed the reduction of the original semi-
crystalline character of CA and CB. MCB membranes
have diffractograms with faster response, indicating a
more amorphous character than MCA. According to Agu-
iar et al. [20], it favors its application as electrolyte in FC
once amorphous structures tend to have superior proton
conductivity. Regarding to reticulation, it couldn’t be said
that it has changed biopolymer’s chains arrangement in

13
Journal of Polymers and the Environment
Fig. 3 FTIR of MCA and MCB membranes
the membranes, which remain similar to neutralized mem-
branes (without reticulation).
Infrared spectroscopy (FTIR) infrared spectrum (Fig. 3)
shows the main absorption bands of MCA and MCB mem-
branes, which are located in: 3500–3300 cm −1, attrib-
uted to axial deformation of hydroxyl and amine groups;
2940–2867 cm−1, corresponding to the C–H stretching;
1641 cm−1, typical amide I band due to carbonyl stretching;
1556 cm−1, related to amide II due to the vibrations in the
NH bond plan and to the CN stretching [21–26]; 1411 cm−1,
corresponding to the CH2 and/or CH3 stretching; next to
1326, 1256 and 1374 cm−1, attributed to the amine I, II
and III stretching, respectively; 1089 and 1035 cm−1, cor-
responding to the C–O–C or COH stretching; and finally
895 cm−1, attributed to the CH deformation out of the plan
[9]. The spectrums of the membranes show similarities
between each other, and all of the observed bands were simi-
lar to those reported in the literature for chitosan membranes
[9, 26]. In this way, it is possible to assert that the reticula-
tion did not change the functional groups which are chitosan
membrane characteristics. However, both MCA and MCB
have a very low transmittance.
Water absorption MCB chitosan membranes had lower
percentage of water absorption (80–160%) than MCA mem-
branes (160–180%). The same effect was observed by Osifo
and Masala [15] and it may be attributed to the greater DD
of the used CB chitosan. This fact can be explained by the
greater number of available amino groups, which promote a
greater occurrence of intermolecular forces existing between
the biopolymer chains, mainly hydrogen bonds between
–OH− and –NH 2 groups, making its three-dimensional
structure more compact. The higher compression hinders
the entry of water molecules in these membranes (Fig. 4). It
might be expected this behavior was even more enhanced in
Fig. 4 MCA and MCB membrane’s water absorption at different tem-
peratures
the reticulated membranes with H2SO4 (MCAR and MCBR).
In other words, the promoted reaction between the reticulat-
ing agent and the amino groups of these membranes would
benefit cross-chain formation and consequently reduce water
absorption [5]. However, there is an opposite behavior in
which the reticulated membranes had higher water absorp-
tion values than the non-reticulated (MCAN and MCBN).
This occurrence can be explained by the fact that cross-chain
formations resulting from the interaction between the proto-
nated amino groups (–NH3+) of chitosan chains (in contact
with acid) and sulfate group SO42−, change the hydrophilic
characteristics of chitosan, attracting water molecules and
promoting membrane swelling. It is important to mention
that since MCB membranes have a higher DD it makes the
recirculation occurs more effectively leading to the observed
difference between the water absorption values of MCBN
and MCBR membranes. Another issue that should be stated
is the fact that reticulation reduces the crystalline domains
of the semi-crystalline structure of chitosan, which can
make the membrane more receptive to water molecules
capture. Furthermore, all membranes showed greater water
absorption rate at the higher temperatures tested (70 °C).
The increase in cell operating temperature directly affects
the electro-osmotic flow mechanism, since with increasing
temperature the pores and channels present in the polymeric
structure of the chitosan membrane expand allowing greater
absorption of water. Therefore, the temperature acts directly
on membrane hydration [5, 7, 27]. Nonetheless, as reported
in the literature, a cell operation at close to 100 °C may
cause dehydration of the membrane making it difficult to
form channels through which the protons would be trans-
ported. Consequently, it might cause the loss of conductivity
[28, 29]. In all assays, the standard deviation values were
below 3%.
13
 Journal of Polymers and the Environment

Proton conductivity proton conductivity was determined -1

10
according to Eq. 4, and it is correlated to the resistance of the MCAR (32
solid electrolyte R. In the Nyquist diagram the point used in MCAN (30
MCBR (47
each graph (Fig. 5) is the one that appears on the real axis (x MCBN (25
axis), in which the resistor is not conditioned to frequency. In

)
-2 - - - Nafion (51
10

other words, the one that at high frequencies Z″ is equal to
zero and Z′ is the actual membrane resistance (R) [19]. The
resistivity of the material is inversely proportional to the pro-
ton conductivity; thus, it is noted that Z′ of MCBN and MCBR
membranes at 60 and 80 °C is between 0 and 1 Ω indicat-
ing higher conductivity values. On the other hand, MCAN e
MCAR membranes showed Z′ between 3 and 10 Ω, indicating
lower conductivity values. The proton conductivity (σ) and the
MCA e MCB membranes thickness at different temperatures
are found in Fig. 6. The thickness of the chitosan membranes
ranged between 25 and 47 µm which are lower values if com-
pared to the ones typically found for Nafion®. For all tested
membranes, the increase in temperature resulted in higher σ
values, as also observed by Luo et al. [30]. The proton con-
ductivity of MCA membranes in general was extremely low
even at higher temperatures. The values were restricted to the
magnitude order of 10−4 S cm−1, far below Nafion®’s conduc-
tivity. Similar results were found by Rahman et al. [24] (10−5
S cm−1 for chitosan and cellulose membranes), Wan et al. [26]
(10−3–10−5 S cm−1 for pure chitosan membranes and phospho-
rylated chitosan membranes) and Vijayalekshmi and Khastgir
[31] (10−4 S cm−1 for pure chitosan membrane and composite
membranes of chitosan/methane sulfonic acid and chitosan/
sodium salt of dodecylbenzene sulfonic acid). The reticula-
tion effect in MCA membranes was not favorable for proton
conductivity, which may be justified due to its smaller amount
of –NH2 groups induced by the low degree of deacetylation of
chitosan CA. As noted by Bispo [32] after reticulation, the pro-
portion of the –NH2 groups available to carry out the proton
-1
Conductivity (S cm
-3
10
-4
10
20 30 40 50 60 70 80
Temperature (°C)
Fig. 6 Proton conductivity (σ) at different temperatures and thickness
(measurement was carried out in seven random points of each mem-
brane using Regmed (electronic equipment) and following the rec-
ommendations of Standard T 411 om-97. The results were expressed
as the arithmetic average of the measurements [33–35]) of chitosan
membranes
exchange is further reduced due to its reaction with reticulating
agent, shown in Fig. 7. Better results of proton conductivity
for MCB membranes (up to a 100 times greater) was achieved
with larger DD and smaller CB chitosan molar mass. It can be
concluded that the greatest amount of –NH2 and its favorable
arrangement in the polymer chain benefited protons conduc-
tion in these membranes, reaching values up to to 1.9 × 10−2 S
cm−1 at 80 °C (same magnitude order of Nafion®). Even con-
sidering the worst MCB membrane result for conductivity, it is
superior to the best MCA result. Unlike the MCA membrane,
reticulation did not negatively influence the conductivity of the
material in MCB membrane due to the larger amount of amino

10
(a) 60 °C (b) 80 °C
MCAR MCAR
8 MCAN MCAN
MCBR MCBR
MCBN MCBN
6

0
0 2 4 6 8 10 0 2 4 6 8 10

Fig. 5 Electrochemical impedance spectroscopy for MCA and MCB membranes at 60 °C (a) and 80 °C (b)

13
Journal of Polymers and the Environment
Fig. 7 Representation of the
crosslinking reaction of chitosan
with sulfuric acid [5]
groups available. It is possible to emphasize that only MCBR
membrane presented an increase in the σ value at temperatures
of 60–80 °C, which may be associated with a better stability
at higher temperatures due to reticulation. Comparing Figs. 5
and 6, it is noted the increase material resistance (Z′) results
in lower proton conductivity values. Table 1 presents some
researches using chitosan membrane as polymer electrolyte.
It is noteworthy, the results for pure chitosan membranes were
originated from studies with composite membranes of chitosan
considering that the preparation of pure chitosan membranes
was performed only for comparison, without exploring the
individual characteristics of chitosan.
Conclusions
Considering the possibility of exploitation and chemi-
cal modifications of its structure, the chitosan obtained
from shrimp farming waste showed to be a very attrac-
tive alternative for researches seeking the development of
proton conductive membranes with performance similar
or higher than Nafion®. The control of the conditions to
obtaining chitosan from the chitin extracted from shrimp
shells allowed membranes for PEMFC to be produced with
superior characteristics compared to commercial. Chitosan
membrane obtained from shrimp shells reached protonic
conductivity values of: 1.6 × 10−2 and 1.9 × 10−2 S cm−1
at 60 and 80 °C, respectively. These results were the clos-
est to the performance achieved by Nafion ® (9.0 × 10 −2
S cm−1), demonstrating potential use as an electrolyte in
PEMFC. It is important to highlight that further assays
should be conducted in future studies in order to deter-
mine the chemical, mechanical and thermal stability of
the membranes.
Acknowledgements The authors gratefully acknowledge PTI Foun-
dation (Brazil) for the financial support and for the granting scholar-
ships (Notice 058/2014 N. 014/2014). We also gratefully Mr. Valdecir
Antônio Paganin from University of São Paulo (USP/IQSC) for provid-
ing the structure and equipment for the research development.
13
 Journal of Polymers and the Environment

Table 1 Performance of chitosan membranes in fuel cells at 25 ± 2 °C

Membrane Degree of deacetyla- Conductivity (S cm−1) References

tion (%)

Chitosan 85 0.009 [5]

Chitosan/polysulfone 0.034
Chitosan/sulphonated polysulfone 0.046
Chitosan/phosphotungstic acid 81 0.00577 [25]
Chitosan/phosphotungstic acid/montmorillonite 0.00225
Chitosan/phosphotungstic acid/montmorillonite/silane 5% 0.00617
Chitosan/phosphotungstic acid/montmorillonite/silane 10% 0.00484
Chitosan/phosphotungstic acid/montmorillonite/silane 15% 0.00292
Chitosan 90 0.0238 [9]
Chitosan/molecular sieves 0.0144–0.0181
Chitosan/PVA 0.0169
Chitosan/PVA/molecular sieves 0.0127–0.0225
Chitosan/TiO2 0.0168
Chitosan/montmorillonites 0.0065–0.0187
Chitosan 95 0.0035 [36]
Chitosan/phosphomolybdic acid 0.015
Chitosan/phosphotungstic acid 0.0122
Chitosan/silicotungstic acid 0.01
Chitosan 80 0.021 [37]
Chitosan/zeolites 0.017–0.020
Chitosan/phosphotungstic acid – 0.018 [38]
Chitosan (2%)/phosphotungstic acid—crosslinked for 30 s – 0.00791 [39]
Chitosan (2%)/phosphotungstic acid—crosslinked for 1 min 0.00807
Chitosan (2%)/phosphotungstic acid—crosslinked for 5 min 0.00649
Chitosan (2%)/phosphotungstic acid—crosslinked for 10 min 0.00688
Chitosan (2%)/phosphotungstic acid—crosslinked for 20 min 0.00742
Chitosan (2%)/phosphotungstic acid—crosslinked for 40 min 0.00877
Chitosan (2%)/phosphotungstic acid—crosslinked for 60 min 0.0104
Chitosan 90 0.0029 [40]
Chitosan/silica supported silicotungstic acid—1 0.0034
Chitosan/silica supported silicotungstic acid—3 0.0039
Chitosan/silica supported silicotungstic acid—5 0.0058
Chitosan/silica supported silicotungstic acid—7 0.0015

– Not specified

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