Applied Surface Science 422 (2017) 406412

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Applied Surface Science

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

Full Length Article

Shield effect of polyaniline between zinc active material and aqueous

electrolyte in zinc-air batteries
Yong Nam Jo a , Suk Hyun Kang a , K. Prasanna a , Seung Wook Eom b , Chang Woo Lee a,
a
Department of Chemical Engineering, College of Engineering, Kyung Hee University, 1732 Deogyeong-daero, Gihung, Yongin, Gyeonggi, 17104, Republic of
Korea
b
Battery Research Center, Korea Electrotechnology Research Institute (KERI), 12 Bulmosan-ro 10 Beon-gil, Seongsan-gu, Changwon 642-120, Republic of
Korea

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

Article history: The self-discharge behavior of zinc-air batteries is a critical issue that is induced by corrosion and hydro-
Received 24 January 2017 gen evolution reaction (HER) of zinc anodes. Polyaniline (PANI) coatings help control the HER and the
Received in revised form 17 May 2017 corrosion reaction. Herein, PANI is synthesized with different amounts of HCl (20, 50, 100 ml). Among
Accepted 4 June 2017
these, the PANI synthesized using 20 ml of HCl (20PANI@Zn) is the most effective for reducing the self-
Available online 6 June 2017
discharge behavior because it provides more amount of coating layer on the surfaces of the zinc particles
compared to other prepared materials. This layer prevents direct contact between zinc and the aqueous
Keywords:
electrolyte and minimize HER. The 20PANI@Zn shows 85% corrosion inhibition efciency against pure
Zinc-air
Polyaniline-coated zinc zinc and results in 97.81% capacity retention after 24 h storage against no-storage condition at ambient
Self-discharge temperature.
Hydrogen evolution reaction 2017 Elsevier B.V. All rights reserved.

1. Introduction
Global warming and the growing demand for energy in mod-
ern society have motivated researchers to study energy conversion
and storage systems. Among the different types of energy storage
systems, Li-ion batteries (LIBs) are most widely used because they
have a high specic energy density, high voltage, and long cycle life
[13]. Nevertheless, LIBs also have some limitations, such as high
cost, toxicity, and use of organic solvents, which can cause safety
concerns [4]. Although LIBs deliver higher specic energy density
compared with other commercialized secondary batteries, the cur-
rent LIB technology is still insufcient for use in electric vehicles.
Metal-air batteries have received much attention as an alternative
to LIBs because they have a higher specic energy density than
most energy storage systems because oxygen gas in ambient air
(the quantity of which is essentially unlimited) is used as a cathode
material [511].
Zinc is one of the most widely used electrodes and has vari-
ous advantages. Namely, it is environmentally benign, abundant,
cheap, easy to handle, stable in aqueous solution, and has a good
electrochemical equivalence of 820 Ah/kg [1215]. In addition, zinc
is safer than lithium and can be fully recycled [6]. Zinc-air batteries
Corresponding author.
E-mail address: cwlee@khu.ac.kr (C.W. Lee).
deliver higher specic energy density compared with other energy
storage systems due to the conguration of the metal-air batter-
ies. The theoretical specic energy density of zinc-air batteries is
1086 Wh/kg [13]. The discharge reactions of the zinc-air battery
are summarized below: [1618]
Anode : Zn + 4OH Zn(OH)4 2 + 2e (1)
Zn(OH)4 2 ZnO + H2 O + 2OH (2)
Cathode : O2 + 4e + 2H2 O 4OH (3)
Overall : 2Zn + O2 2ZnO (4)
Zinc-air secondary batteries can be classied into two cate-
gories: electrically rechargeable and mechanically rechargeable
systems. Electrically rechargeable zinc-air batteries have disadvan-
tages including dendrite formation during the recharging process,
a limited cycle life, and the hydrogen evolution reaction (HER),
which is due to the more negative reduction potential of zinc than
of hydrogen. The HER leads to self-discharge of zinc-air batteries.
The dendrite formation and limited cycle life issues can be
solved by employing a mechanically rechargeable zinc-air battery.
However, HER cannot be reduced merely by changing the sys-
tem. During the HER, the metal undergoes anodic dissolution, with
cathodic evolution of hydrogen in an aqueous solution. The cor-
rosion potential of the metal in an aqueous solution is a mixed
potential that includes the partial oxidation reaction. In other

http://dx.doi.org/10.1016/j.apsusc.2017.06.033
0169-4332/ 2017 Elsevier B.V. All rights reserved.
 Y.N. Jo et al. / Applied Surface Science 422 (2017) 406412
Fig. 1. The FTIR spectra of PANI@Zn materials prepared with three different amount
of HCl.
words, in the anodic direction, anodic dissolution occurs according
to the reaction shown below: [19,20]
Zn + 4OH Zn(OH)4 2 + 2e
The partial reduction reaction can also occur, which is the HER
in an alkaline solution:
2H2 O + 2e 2OH + H2
The HER in the zinc-air battery is given as: [8,16,17]
Zn + 2H2 O Zn(OH)2 + H2
In order to overcome the corrosion of zinc anodes and sup-
press the HER, Lee et al. introduced zinc alloys and acid additives to
reduce dendrite formation and raise the hydrogen overpotential of
zinc-air batteries [14,21]. Zhang et al. reported that introducing Bi
and Ca into a pasted zinc electrode improved the discharge behavior
[22]. Ein-Eli et al. introduced polyethylene glycol (PEG) as an elec-
trolyte additive for corrosion inhibition [23]. Kim et al. reported that
suppression of ZnO formation is advantageous, decreasing both
resistance and hydrogen evolution in zinc-air secondary batteries
[24].
Among the intrinsically conducting polymers, polyaniline
(PANI) was found to be most interesting because of its wide range
of conductivity, high stability, tunable property, low cost, and ease
of synthesis [25,26]. In general, PANI is synthesized by chemical or
electrochemical oxidative polymerization of monomers. In addi-
tion, plasma, electroless, and solid-state polymerization methods
have also been reported [2729]. Conventionally, irregular PANI is
synthesized by dropwise addition of ammonium persulfate (APS)
into aniline while stirring. The sonochemical process is similar to
the conventional process, initiated with dropwise addition of an
APS solution to an aniline solution. The quality and uniformity of
synthesized PANI are affected by the acid concentration during syn-
thesis. Lower concentrations of acid result in lower yields of nal
product [30,31].
In this paper, we synthesized PANI using the sonochemi-
cal method with different amounts of HCl. We also synthesized
PANI-coated zinc to suppress the self-discharge behavior, inhibit
corrosion reactions and the HER in zinc-air batteries.
2. Experimental
The coating material PANI was synthesized using a sonochem-
ical method. First, acidic aniline solution was prepared by adding
1.86 g of aniline to a beaker containing 20, 50, and 100 ml of 1 M
407
Fig. 2. XRD patterns of the PANI coated on zinc materials.
Table 1
Corrosion parameters.
Materials Ecorr (V) Icorr (mA/cm2 )  (%)
Zn 1.399 3.836
(5) 20PANI@Zn 1.395 0.591 85
50PANI@Zn 1.403 1.115 71
100PANI@Zn 1.397 1.267 67
(6)
hydrochloric acid (HCl), respectively. This solution was sonicated
in an ultrasonic bath at 50 kHz using a power of 100 W. Then, 1.14 g
(7) of APS was separately dissolved in 20, 50, and 100 ml of 1 M HCl
solution, and this was added dropwise to the 20, 50, 100 ml of
acidic aniline solution, respectively, during this reaction temper-
ature was maintained at 2 C. After the addition of the acidic APS
solution, 20 g of zinc was added, and the mixture was kept in an
ultrasonic bath for 30 min. After sonication, the powder was col-
lected in a Bchner funnel using a water aspirator. The precipitate
cake was ltered and washed with deionized water and ethanol
until the ltrate became colorless. In addition, washed materials
were dried at 60 C under vacuum overnight. The synthesized PANI-
coated zinc materials with 20, 50, and 100 ml of acidic aniline and
acidic APS solution were designated as 20PANI@Zn, 50PANI@Zn,
and 100PANI@Zn, respectively.
The zinc-air battery consisted of a top cover with holes, an air
cathode (ADE-75, MEET), a separator (Celgard 3401), an electrode
container, a Cu current collector, and a bottom cover. To fabricate
the gel electrolyte, a 7 M aqueous solution of KOH was mixed with
2 wt% polyacrylic acid (PAA). Then, 0.6 ml of the gel electrolyte was
mixed with 0.6 g of the synthesized material, which was located in
an electrode container having length, width, and height dimensions
of 2.5, 2, and 0.1 cm, respectively. The electrochemical discharge
behaviors were characterized at room temperature using a bat-
tery cycler (BaTester 05001, HTC) at a 100 mA current and a 0.2 V
cut-off voltage. A 60-min rest time allowed the gelled electrolyte
to soak in the active materials. To characterize the self-discharge
behavior, the materials were analyzed immediately after cell fabri-
cation and after being stored at room temperature for 24 h without
any treatment. Tafel extrapolation was performed using an electro-
chemical analyzer (COMPACTSTAT, IVIUM technologies), and the
electrochemical cell was composed of an Hg/HgO reference elec-
trode, a platinum wire as a counter electrode, and the working
electrode. The crystallinity of the coated materials was character-
ized using an X-ray diffractometer (XRD, D8 Advance, Bruker) using
Cu K radiation over a scattering angle range of 10 to 80 . The mor-
phology was determined using a eld emission scanning electron
microscope (FE-SEM, LEO SUPRA 55, Carl Zeiss) and a transmission
408 Y.N. Jo et al. / Applied Surface Science 422 (2017) 406412
Fig. 3. FE-SEM images of the pristine zinc and PANI@Zn materials with different amount of HCl: (a) Zinc, (b) 20PANI@Zn, (c) 50PANI@Zn, (d) 100PANI@Zn.
electron microscope (FE-TEM, JEM-2100F, JEOL). Energy disper-
sive X-ray (EDX) mapping was conducted using a FE-TEM/EDX
(Oxford, INCA). The coating materials (PANI) were conrmed using
a Fourier transform infrared spectrometer (FTIR, Spectrum One
System, Perkin-Elmer) recorded between 500 cm1 and 4000 cm1
from KBr pellets.
3. Results and discussion
3.1. FTIR and XRD characterization
Fig. 1 shows the FTIR spectra of PANI@Zn materials prepared
with three different amounts of HCl. The spectra were recorded
in the wave number range of 5004000 cm1 . As shown, the PANI
was well synthesized and coated on the zinc particle. The peaks
observed in the spectra correspond well to PANI, as previously
reported [3234]. A broad peak around 3440 cm1 is associated
with the N H stretching of PANI. The peaks at 1597 cm1 and
1497 cm1 are due to the quinoid structure and benzenoid struc-
ture of PANI, respectively. The peak at 1286 cm1 is evidence of
the C N stretch of the benzenoid ring. The peak at 809 cm1 cor-
responds to the C H out-of-plane bending vibration.
Fig. 2 shows XRD patterns of PANI-coated zinc materials. All of
the diffraction peaks for PANI@Zn materials were in good agree-
ment with the standard data for hexagonal crystal structures of zinc
(JCPDS#87-0713). In addition, the coating material (PANI) did not
affect the original zinc structure, and there were no peaks related
to PANI due to its amorphous structure.
3.2. Morphology characterization
In order to conrm the PANI coating thickness and uniformity
on the surface of zinc particles, we conducted FE-SEM and FE-TEM
analyses of PANI@Zn materials. The FE-SEM and FE-TEM images of
PANI@Zn materials are shown in Figs. 3 and 4, respectively. Fig. 3
shows the FE-SEM images of the pristine zinc and PANI@Zn mate-
rials with different amounts of HCl. As shown, the particle sizes of
the PANI@Zn materials depended on the size of the zinc particle. In
addition, we conrmed that the PANI were well coated on the zinc
surface. As shown in Fig. 3(b), more angular-shaped PANI particles
were observed on the zinc compared to other PANI@Zn materials
and pure zinc.
Fig. 4 shows the FE-TEM images of the various PANI@Zn sam-
ples and their corresponding magnied images. As shown in Fig. 4,
there were distinct contrast differences in the images, which con-
rmed the existence of two phases, amorphous PANI and zinc
particles. Lower HCl concentration resulted in lower fraction of nal
products, and the uniformity of the PANI was affected by the acid
concentration [33,35]. In addition, if the concentration of aniline
and APS is high, reactions for continuous formation and agglom-
eration of PANI could be operative [36]. In this study, 1 M HCl was
used for preparation of PANI, and the amount of HCl was varied. A
decrease in the amount of HCl resulted in a thicker coating layer.
In other words, increasing the aniline concentration in the HCl
solution led to a thicker coating layer. In addition, we observed
partial coating of the PANI on zinc with increasing HCl content.
It is indicated that, when the concentration of aniline and APS is
 Y.N. Jo et al. / Applied Surface Science 422 (2017) 406412 409

Fig. 4. FE-TEM images of PANI@Zn: (a) 20PANI@Zn, (b) 50PANI@Zn, (c) 100PANI@Zn; corresponding magnied images: (d) 20PANI@Zn, (e) 50PANI@Zn, (f) 100PANI@Zn.

Fig. 5. (a) SAED pattern and EDX mappings of 100PANI@Zn: (b) electron image; (c) an overlay of Zn, C and N maps; (d) elemental mapping of Zn; (e) elemental mapping of
C; (f) elemental mapping of N.

increased, the PANI formed thicker coating layer on the zinc surface. conrm the presence of zinc. Fig. 5 (a) shows the SAED patterns
The uniformity and thickness of the PANI coating layer inuenced of 20PANI@Zn and the diffraction patterns could be assigned to
the self-discharge behaviors of the zinc-air battery. The selected the (101), (102), (103), and (112) planes of zinc hexagonal struc-
area electron diffraction (SAED) measurement was performed to ture. These results are consistent with the results obtained from
410 Y.N. Jo et al. / Applied Surface Science 422 (2017) 406412
Fig. 6. The polarization curves obtained for zinc and PANI@Zn materials in a 7 M KOH solution: (a) Zinc, (b) 20PANI@Zn, (c) 50PANI@Zn, (d) 100PANI@Zn.
the XRD pattern (Fig. 2). Therefore, it was identied that the core
particle of the prepared material was zinc. Further, EDX mapping
of the 100PANI@Zn conrmed that the core of the particle shown
in Fig. 5(d) was zinc. Overlaying carbon and nitrogen signals from
the PANI coating material were also observed, conrming that PANI
was well coated on the zinc surface.
3.3. Tafel extrapolation
To identify the effect of coating material on corrosion behav-
ior, we measured the polarization behavior of each coated material
using a three-electrode system. Polarization curves obtained for
zinc and PANI@Zn materials in a 7 M KOH solution are shown in
Fig. 6. These curves have similar behaviors but different corro-
sion parameter values including corrosion current density (Icorr ),
corrosion potential (Ecorr ), and corrosion inhibition efciency, ().
In general, the cathodic region is related to the hydrogen evolu-
tion reaction, and zinc dissolution occurs according to Eq. (5), with
increasing potential in the anodic direction. The dissolution of zinc
continues with increasing potential until the zincate concentration
reaches a critical point [37]. The corresponding corrosion parame-
ters derived from the anodic and cathodic branches shown in Fig. 6
are summarized in Table 1 along with the corrosion inhibition ef-
ciency. The corrosion inhibition efciencies were obtained from the
following expression:
Icorr Icorr
= 100
Icorr
where Icorr and Icorr are the corrosion current densities of zinc and
the coated material, respectively.
Fig. 6 and Table 1 show that the corrosion potential values
of PANI@Zn materials were similar to that of zinc. However, the
PANI@Zn materials had lower corrosion current density values than
that of zinc. This result indicates that PANI coating can prevent
the corrosion of zinc particles in KOH solution. The lower corro-
sion current density could possibly be explained by the prohibition
of electrolyte diffusion throughout the zinc particles due to the
overlying PANI. Therefore, the corrosion reaction was inhibited by
the PANI coating. As such, we expected suppressed self-discharge
behaviors with 20PANI@Zn than with the other PANI@Zn materials
as well as with uncoated zinc.
3.4. Electrochemical discharge behavior
Suppressing the corrosion reaction and HER is a critical issue for
primary and secondary zinc-air batteries because these reactions
lead to self-discharge of zinc-air batteries. The energy density of
the zinc-air battery mostly depends on utilization of zinc anodes,
which cannot be fully utilized due to these reactions in alkaline
solution. The corrosion reaction and HER should be inhibited as
much as possible in order to enhance the discharge ability of zinc-
air batteries.
To characterize the self-discharge behavior of PANI@Zn materi-
als, the materials were analyzed immediately after cell fabrication
(9) and after being stored at room temperature for 24 h without any
treatment. The value of capacity retention was calculated after 24 h
 Y.N. Jo et al. / Applied Surface Science 422 (2017) 406412 411

pared with other PANI@Zn materials. These results corresponded

well with the results of the Tafel extrapolation.

4. Conclusions

The conductive polymer PANI was synthesized using different

amounts of HCl and was coated onto zinc in order to inhibit the cor-
rosion reaction and the HER. We conrmed from FTIR that PANI was
well synthesized. The morphology characterization results con-
rmed the coating of PANI onto the zinc surface. The 20PANI@Zn
was the most effective material for reducing self-discharge among
the attempted materials in this work. The increasing concentra-
tion of aniline and APS in HCl lead to thicker and uniform coating
layer on the surface of zinc particles and it lead to enhance capacity
retention of 20PANI@Zn. In addition, PANI coating layer prevented
direct contact between zinc and KOH electrolyte and minimized
the corrosion reaction and the HER. Also, the other PANI@Zn mate-
rials also showed suppressed self-discharge behaviors compared
with the pristine zinc anodes. We therefore conclude that PANI-
coated materials are promising anode materials for use in zinc-air
batteries.

Acknowledgment

This work was supported by the next generation secondary

battery R&D program of MOTIE/KEIT. [10042575, Development of
5 kW Zn-air battery for EV and 3.3V-1,000F pouch type high-power
supercapacitor]

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