International Journal of Precision Engineering and Manufacturing-Green Technology (2020) 7:505–509 Online ISSN 2198-0810

https://doi.org/10.1007/s40684-019-00136-y Print ISSN 2288-6206

SHORT COMMUNICATION

Effect of Zn Addition on Electrochemical Performance of Al–Air Battery

Hansol Lee1 · Timothy Alexander Listyawan2 · Nokeun Park2 · Guntae Kim1 · Ikwhang Chang3

Received: 10 December 2018 / Revised: 28 June 2019 / Accepted: 2 July 2019 / Published online: 31 July 2019
© Korean Society for Precision Engineering 2019

Abstract
We investigate the effect of Zn addition on an Al–air battery at the anode. The tested Al–air battery consists of a 6 mol%
potassium hydroxide (KOH) electrolyte, a fiberglass separator, and a Pt/C + IrO2 cathode. The Zn-added Al(Al60Zn40)–air
battery shows a higher power density of 48 mW/cm2, while a pure Al–air battery exhibits a power density of 38 mW/cm2.
Approximately, 30 charge/discharge cycles of the Al–air battery were performed, while ~ 71 cycles of the ­Al60Zn40–air bat-
tery were performed. Adding Zn to the Al–air battery improves its electrochemical performance and the number of charge/
discharge cycles can be significantly increased.

Keywords Al–air · Zn · Power density · Cycle · Electrochemical performance

1 Introduction for electric vehicles because of its high theoretical energy

A metal–air battery is a direct energy conversion storage
device that converts chemical energy into electrical energy,
and it is operated at room temperature and in an ambient
environment [1–3]. A metal oxidation reaction occurs at the
anode while an oxygen reduction reaction (ORR) occurs
at the cathode, where metal ions, electrons, and oxygen
interact [4]. Various metal–air batteries have been actively
developed for electric vehicles as well as energy storage sys-
tems [5, 6]. As one of the metal–air batteries, the aluminum
(Al)–air battery is an attractive candidate as a power source
* Nokeun Park
nokeun_park@yu.ac.kr
* Guntae Kim
gtkim@unist.ac.kr
* Ikwhang Chang
ikwhang2@wku.ac.kr
1
Department of Energy and Chemical Engineering,
Ulsan National University of Science and Technology,
50 UNIST‑gil, Eonyang‑eup, Ulju‑gun, Ulsan 44919,
Republic of Korea
2
School of Material Science and Engineering, Institute
of Materials Technology, Yeungnam University,
280 Daehak‑ro, Joyeong‑dong, Gyeongsan,
Gyeongsan gbuk‑do 38541, Republic of Korea
3
Department of Automotive Engineering, Wonkwang
University, 460 Iksan‑darero, Iksan, Jeonbuk 54538,
Republic of Korea
density (8100 Whkg−1), which is significantly greater than
that of state-of-the-art lithium–ion batteries [7]. The chemi-
cal reactions of the Al–air battery are as follows:
Al + 3OH − → Al(OH)3 + 3e− + 2.31V (1)
O2 + 2H2 O + 4e− → 4OH − + 0.40V (2)
4Al + 3O2 + 6H2 O → 4Al(OH)3 + 2.7V (3)
where (1) and (2) reactions occur at the anode and at the
cathode, respectively, and (3) is the total reaction. The nomi-
nal voltage of a typical Al–air battery using a potassium
hydroxide electrolyte is ~ 1.2 V. However, some technical
and scientific barriers preventing the scaling-up of Al–air
batteries have yet to be overcome [3]. Zinc (Zn)–air batteries
are also century-old electrochemical cells but have recently
attracted the attention of many researchers [8]. Zn–air bat-
teries can store more energy at a fraction of the cost and be
more easily fabricated compared with lithium–ion batteries.
Thus, we believe that Zn–air batteries are one of the viable
alternative options for electric vehicles [9, 10]. The target
performance of the metal–air battery for electric vehicle
market is a single charge range of more than 500 km and
lifespan of 8-year/100,000-mile warranty [11, 12]. Many
studies reported new catalysts for enhancing oxygen reduc-
tion and oxygen evolution reactions at the cathode [13–16].
However, general metals at the anode are alloys which are
used for their corrosion-resistance, ultra-high strength, low
weight, and other properties [5, 6, 17–24]. We believe that

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506 International Journal of Precision Engineering and Manufacturing-Green Technology (2020) 7:505–509
the electrochemical performance and behavior of metals at
the anode have not been studied sufficiently. Recently, Park
et al. analyzed the effect of adding Zn and indium (In) to
an Al–air battery at the anode in terms of its self-corrosion
rate, open-circuit voltage, and discharge characteristics [25].
They found that the addition of In at the anode reduces the
growth of a Zn passivation layer, improving the discharge
performance of the Al–air battery [25]. Lee et al. used an
Al–air battery with foil to maximize the surface area of the
anode by a micro-sand blasting method [3]. Consequently,
the energy capacity of the Al–air battery with foil was five
times greater than that of the Al–air battery without foil [3].
In this paper, we performed electrochemical measure-
ments and characterization to investigate the effect of add-
ing Zn to the Al–air battery. Consequently, we found that
the addition of Zn to Al metal significantly improves the
electrochemical performance and charge/discharge capacity
of the Al–air battery.
2 Experimental
2.1 Sample Preparation
Figure 1 shows the process flow of ­Al60Zn40 (Al:Zn = 60:40),
in which ingots were fabricated in a tube furnace using Al
shot (Part#:00632, Alfa Aesar) and Zn shot (Part#:10440,
Alfa Aesar) with 99.9% and 99.99% purity, respectively.
The melting and pouring temperatures were approximately
at 750 °C under a gas mixture of 97% argon (Ar) and 3%
hydrogen ­(H2). Al and Zn shots were melted in an alumina
­(Al2O3) crucible in the furnace to remove slag layers of
molten metal. Hand-stirring was performed every 20 min
until the Al and Zn melted, and then it was poured into a
copper mold. Finally, to obtain uniform samples, cylindrical
ingots of Al and A ­ l60Zn40 (diameter: 15 mm) were cold-
rolled until their thickness was reduced by 30%. The samples
were mechanically polished using #1500 SiC paper and then
formed into a cylindrical shape with a diameter of 10 mm
and a thickness of 1 mm.
Fig. 1  A process flow of ­Al60Zn40 sample: mechanical mixing, melting, cold-rolling (thickness reduction), and electrochemical testing
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2.2 Electrochemical Set‑Up and Testing
The rechargeable metal–air battery was fabricated as a coin-
type battery (CR2032, MTI). 6 mol% KOH was used as the
electrolyte to form zincate ions. Glass fiber (ECC1-01-0012,
MTI) and Pt/C + IrO2 were used as the separator and for the
cathode, respectively. The catalyst at the cathode was coated
on teflon-coated carbon paper by an electrospray method.
First, the Pt/C + IrO2 (Pt/C: ­IrO2 = 1:1) was dissolved in
ethanol and isopropyl alcohol with 5 wt% Nafion solution
(Part#: 274704, Sigma-Aldrich). Second, the catalyst solu-
tion was placed in a syringe with a positively charged capil-
lary tip. A voltage of 8 kV was applied between the syringe
needle tip and the carbon paper using a high-voltage–power
supply (Korea Switching, Korea). The composite droplets
were electro-sprayed from the needle at 3.0 ml/h and col-
lected on the aluminum foil. Finally, the solvent (ethanol
and isopropyl alcohol) was dried at room temperature before
the cell test, and the catalyst loading density was 1 mg/cm2.
Polarization curves were obtained by linear sweep voltage
at a scan rate of 10 mV/s from open circuit voltage (OCV)
to 0 V.
X-ray diffraction (XRD) analysis was performed between
30° to 90° with a voltage of 40, mA current of 30, and a
step size of 0.026°. The XRD analysis was conducted to
determine the phase of samples using PAN analytical X’pert
high-score software. The microstructure was characterized
by electron backscatter diffraction (EBSD, DigiView detec-
tor) and examined using a secondary electron microscope
(SU-70, Hitachi).
3 Results and Discussion
3.1 Characterizations
Figure 2 shows the XRD results of the Al and ­Al60Zn40
samples. According to the XRD analysis, the Al samples
have an Al face-centered cubic (FCC) structure while the
International Journal of Precision Engineering and Manufacturing-Green Technology (2020) 7:505–509
Fig. 2  XRD result of Al and A
­ l60Zn40
­Al60Zn40 samples have FCC and hexagonal close-packed
(HCP) peaks. This indicates that the addition of Zn to pure
Al promotes the formation of the secondary phase on the
microstructure, as the secondary phase has been predicted
by the phase diagram of ­Al60Zn40 [26, 27].
As shown in Fig. 3, the microstructures of the after-tested
samples were also characterized by EBSD to measure the
effect of adding Zn to Al. Figure 3a shows the microstructure
of Al, which is slightly elongated. Figure 3b shows an image
quality map of A­ l60Zn40 in two different phases of FCC and
HCP. The two phases FCC and HCP are consistent with the
XRD result. The FCC phase of A ­ l60Zn40 is marked in a green
area with a volume fraction of approximately 66% because
HCP, as a secondary phase, interrupted the grain boundary
migration of FCC on the microstructure as it has been pre-
dicted by the phase diagram of ­Al60Zn40 [26, 27].
3.2 Electrochemical Performance
Figure 4 shows the I–V–P results of the metal–air bat-
teries using the Al sample and the A­ l60Zn40 sample. The
­Al60Zn40–air battery exhibits a higher power density than
the Al–air battery. The Al–air battery could not achieve
a power density over 38 mA/cm 2. The ­A l60Zn40 battery
is more stable in an alkaline KOH electrolyte while the
Fig. 3  EBSD analysis of a Al and b ­Al60Zn40
507
Fig. 4  Current–voltage–power density measurements of Al–air and
­Al60Zn40–air batteries
Al battery has a relatively high self-corrosion rate. The
maximum power densities of the Al–air battery and
­Al60Zn40–air battery are 48 and 38 mW/cm2, respectively.
The Al oxidation leads to Al(OH4) formation at the anode.
Ma et al. reported that the addition of Zn to the Al alloy
anode improves the electrochemical performance of the Al
alloy–air battery during the first 300 min [28]. The results
of Ma are consistent with our experimental result. Also,
the Al–air has a voltage drop of − 1.66 V, which is lower
than the voltage drop of ­Al60Zn40–air battery (~ − 0.76 V).
The initial voltage of the Al–air is higher than that of the
­Al60Zn40–air battery. However, for the Al–air cathode, the
self-corrosion occurs rapidly when immersed in an alka-
line electrolyte. Zn is relatively stable in the alkaline state
as compared with Al, so the corrosion loss is very low.
Therefore, the voltage drop of the Al–air are greater than
that of the A­ l60Zn40–air battery at the high current density.
As shown in Fig. 5, discharge/charge cycle tests of two
samples were conducted under 1 mA/cm2. The cycle capa-
bility of the ­Al60Zn40–air battery was ~ 71 cycles while
the Al–air battery’s cycle capability was approximately
~ 30 cycles. The number of discharge/charge cycles of
the ­A l 60Zn 40–air battery can undergo two times higher
than that of the Al–air battery, which demonstrates that
the addition of Zn is key in improving the discharge/
charge cycle performance. The Zn addition in Al alloy
anode improves the electrochemical performances during
300 min in Al alloy–air battery [28]. Ma’s works is an
excellent agreement with our experimental result. Also, we
believe that Zn addition in anode metal reduces the forma-
tion of Zn passivation layer of adsorption and desorption,
and the thinner passivation layer improve the discharge/
charge capabilities [25].
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508 International Journal of Precision Engineering and Manufacturing-Green Technology (2020) 7:505–509
Fig. 5  Discharge and charge cycling properties of Al–air and
­Al60Zn40–air
4 Conclusions
We investigated the effect of the addition of Zn on the elec-
trochemical and charge/discharge cycle performance of the
Al-based metal–air battery. We demonstrated that the Zn
addition significantly improves the maximum power density
and the cycle performance. The cycle performance of the
Al–air battery with Zn is more than two times higher than
that of the Al–air battery without Zn. We will perform more
detailed quantitative studies to find optimal Al:Zn ratios for
batteries at the anode.
Acknowledgements This work was supported by National Research
Foundation of Korea Grant funded by the Korean Government (NRF-
2018-Global Ph.D. Fellowship Program, and 2017R1C1B5018183).
Also, This research was supported by the Mid-Career Researcher Pro-
gram (NRF-2018R1A2A1A05077532) through the National Research
Foundation (NRF) of Korea, funded by the Ministry of Science, Sci-
ence, ICT and Future Planning.
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include materials for new energy
Publisher’s Note Springer Nature remains neutral with regard to technologies and their applica-
jurisdictional claims in published maps and institutional affiliations. bility in powering or conversion,
storage devices. A particular
field of interest is the develop-
ment of layered perovskite
Hansol Lee received her bache- oxides for fuel cell applications,
lor’s degree in energy conversion metal-air batteries, proton-con-
and storage and chemical engi- ducting oxides for SOFCs, and oxygen membrane reactors.
neering from Ulsan Institute of
S c i e n c e a n d Te ch n o l o g y Ikwhang Chang obtained his
(UNIST), Republic of Korea. Ph.D. in department of intelli-
She is currently a Ph.D. candi- gent convergence systems from
date in Department of Energy Seoul National University in
Engineering at UNIST. Her 2015. He is an assistant professor
research interests lie in electro- in the department of automotive
chemical catalysts based on lay- engineering, Wonkwang univer-
ered perovskites and their micro- sity, Republic of Korea. His
st r u c t u ra l a n a lys i s u s i n g research interests include a
transmission electron micros- design of energy system using
copy and pulsed laser deposition, fuel cells, and batteries.
aiming to develop efficient
energy storage and conversion devices, such as metal-air batteries and
water splitting.

Timothy Alexander Listyawan is

affiliated with Yeungnam Uni-
versity, South Korea. He
obtained Bachelor of Engineer-
ing degree from Universitas
Indonesia, Indonesia and Curtin
University, Australia with a
major of materials and metallur-
gical engineering. He then
moved to South Korea and
became Ph.D. candidate at
Yeungnam University. His
research is mainly but not lim-
ited to multiple-principle and
high entropy alloy.

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