Journal of Power Sources 332 (2016) 330e336

Contents lists available at ScienceDirect

Journal of Power Sources

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

Durable rechargeable zinc-air batteries with neutral electrolyte and

manganese oxide catalyst
Afriyanti Sumboja a, Xiaoming Ge a, Guangyuan Zheng a, F.W. Thomas Goh a,
T.S. Andy Hor a, b, Yun Zong a, **, Zhaolin Liu a, *
a
Institute of Materials Research and Engineering (IMRE), A*STAR (Agency for Science, Technology and Research), 2 Fusionopolis Way, Innovis, #08-03,
138634, Singapore
b
Department of Chemistry, The University of Hongkong, Pokfulam Road, Hong Kong, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

ORR and OER of MnOx bifunctional

catalyst in chloride-based electrolyte.

pH-dependent electrocatalytic activ-
ity of MnOx.

Rechargeable Zn-air battery was sta-
ble during three-months of cycling
test.

Method to eliminate carbon corro-
sion in air cathode and carbonation
in electrolyte.

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

Article history: Neutral chloride-based electrolyte and directly grown manganese oxide on carbon paper are used as the
Received 22 July 2016 electrolyte and air cathode respectively for rechargeable Zn-air batteries. Oxygen reduction and oxygen
Received in revised form evolution reactions on manganese oxide show dependence of activities on the pH of the electrolyte. Zn-
7 September 2016
air batteries with chloride-based electrolyte and manganese oxide catalyst exhibit satisfactory voltage
Accepted 23 September 2016
profile (discharge and charge voltage of 1 and 2 V at 1 mA cm2) and excellent cycling stability (z90
days of continuous cycle test), which is attributed to the reduced carbon corrosion on the air cathode and
decreased carbonation in neutral electrolyte. This work describes a robust electrolyte system that im-
Keywords:
Zn-air batteries
proves the cycle life of rechargeable Zn-air batteries.
Neutral electrolyte © 2016 Elsevier B.V. All rights reserved.
Manganese oxide
Electrocatalyst
Rechargeable metal-air batteries

1. Introduction air batteries are promising candidate for large-scale energy stor-
age as they offer higher energy density, better safety, and lower cost
Battery is one of the key enablers in large-scale adoption of than most of the currently available battery technologies [1,2].
renewable energy resources. Metal-air batteries, in particular Zn- Although primary Zn-air batteries have been well developed, suc-
cessful applications of secondary Zn-air batteries are hindered by
the various technical hurdles. The most notable challenge in
* Corresponding author. advancing rechargeable Zn-air batteries is to improve their cycle
** Corresponding author. life, which can be affected by the choice of air cathode, Zn anode,
E-mail addresses: y-zong@imre.a-star.edu.sg (Y. Zong), zl-liu@imre.a-star.edu.sg and electrolyte [3,4]. Researches on Zn-air batteries have been
(Z. Liu).

http://dx.doi.org/10.1016/j.jpowsour.2016.09.142
0378-7753/© 2016 Elsevier B.V. All rights reserved.
 A. Sumboja et al. / Journal of Power Sources 332 (2016) 330e336
focused on synthesizing efficient bifunctional catalysts for air-
cathode and stable zinc for anode [5e8]. Limited attention was
paid to the electrolyte, which has a significant impact on the cycle
life of the batteries. Potassium hydroxide (KOH) has been primarily
used as the electrolyte for Zn-air batteries due to its excellent ionic
conductivity, high oxygen diffusion coefficient, low viscosity, as
well as good activity for both Zn anode and air cathode [3,9].
Despite its desirable properties, the usage of KOH in Zn-air batteries
raises several technical problems [3,4,10,11]. The first problem is
associated with the corrosion of carbon-based air cathode in
concentrated alkaline electrolyte which may proceed via following
reaction [12,13]:
C þ 6OH / CO2
3 þ 3H2O þ 4e

Carbon in the air cathode is oxidized to carbonate ions and
dissolves into the electrolyte. Continuous oxidation of carbon in
alkaline electrolyte also results in brown colored electrolyte due to
the formation of carboxylic acids, such as mellitic acid and humic
acid [14,15]. Therefore, it is desirable to reduce the pH of the elec-
trolyte to improve the long-term stability of Zn-air batteries with
carbon-based air cathode. Another problem is related to the for-
mation of insoluble K2CO3 arising from the reaction of aerial CO2
with KOH. The carbonate will eventually precipitate out, resulting
in electrolyte consumption and reduction in electrolyte conduc-
tivity. Precipitates may also block the pores within the air cathode,
causing gradual passivation of the air cathode, and degrading the
long-term performance of the batteries [2,10,11].
Neutral electrolytes are environmentally friendly and able to
remediate the corrosion problem related to the use of alkaline or
acidic electrolytes. They are also attractive for biofuel and biosensor
applications, which are sensitive to extreme pH environments [16].
Despite these advantages, metal-air batteries with aqueous neutral
electrolyte have been rarely reported. Amendola et al. [17]
demonstrated that Zn-air batteries with near-neutral electrolyte
showed discharge and charge voltage of 0.9 and 2.1 V. Goh et al. [11]
studied the reaction mechanism of Zn and air cathode in chloride-
based electrolyte, revealing that oxygen reduction reaction (ORR)
and oxygen evolution reaction (OER) in air cathode are more
sluggish than Zn dissolution/deposition in anode.
Chloride-based electrolyte is preferred due to its sufficiently
high buffering capacity, good conductivity, and absence of elec-
trolyte carbonation [10,18]. It has been widely used in electro-
plating of Zn to replace the toxic cyanide bath [19]. Furthermore,
instead of using conventional method of physical mixing and
coating of powder-based catalyst on air cathode, we grow amor-
phous MnOx catalyst directly on carbon paper air cathode. This
method effectively reduces contact resistance, improves discharge/
charge profile, and enhances the cycle life of Zn-air batteries [20].
MnOx is an attractive catalyst in neutral chloride-based electrolyte
due to its abundance and environmental friendliness. It has high
selectivity towards oxygen evolution instead of chlorine evolution
reaction, and hence effectively prevented the generation of chlorine
gas [17,21,22]. Although its catalytic activity has been widely
investigated in alkaline medium [23,24], limited studies have been
carried out in neutral pH and they were mainly reported for mi-
crobial fuel cell application [25,26]. Combining the advantage of
directly grown MnOx catalyst, neutral pH electrolyte is expected to
enhance the cycle life of Zn-air batteries. Rechargeable Zn-air bat-
teries with directly grown MnOx catalyst and chloride-based elec-
trolyte show excellent stability for up to 90 days, far exceeding the
stability of the same batteries tested in alkaline electrolyte (z41
days). Electrochemical studies were performed to investigate the
electrochemistry of oxygen in chloride-based and alkaline elec-
trolytes. Material characterizations suggest the failure of Zn-air
331
batteries with alkaline electrolyte is associated with the corrosion
of carbon-based air cathode and carbonation of alkaline electrolyte.
2. Experimental
MnOx grown on carbon paper was synthesized according to our
previous report [20]. In brief, carbon paper (10 BN SGL Carbon, size
2  2 cm2) was immersed into the solution containing 0.5 mmol of
Mn(NO3)2in 10 ml ethanol for 15 min, and was left partially dried in
the air for 60 s. It was then immersed into a mixture of 10 ml 0.1 M
KMnO4 and 10 ml 0.1 M H2SO4 for 30 min while stirring at room
temperature. The sample was rinsed with DI water and baked at
180  C over 24 h in an oven.
Rotating disc electrode (RDE) in three-electrode set-up was used
to investigate catalytic activity of directly grown MnOx on carbon in
different type of electrolytes (i.e. 0.1 M NH4Cl, 0.1 M NH4Cl pH 7, or
0.1 M KOH). NH4OH was used to adjust the pH of NH4Cl to 7.
Working electrode was prepared by casting MnOx catalyst ink onto
5 mm diameter RDE tip (Metrohm). The ink was prepared by
crushing directly grown MnOx on carbon paper into powder. The
powder (9 mg) and carbon black (2.25 mg) were ultrasonically
dispersed into 2.4 ml of H2O:IPA:Nafion solution (ratio:
2.5:1:0.094) to form catalyst ink. Appropriate amount of the ink
was dripped onto RDE tip to achieve loading of 0.1 mg cm2. RDE,
platinum counter electrode, and Ag/AgCl (3 M KCl) reference
electrode were connected to potentiostat (Autolab PGSTAT302N)
and immersed into electrolytes that were purged by O2 or N2 gas.
Electrochemical activity of the catalyst was studied via cyclic vol-
tammetry (CV) and linear sweeping voltammetry (LSV) with
sweeping rates of 5 mV s1 at various rotating speeds. Potential
scale was calibrated to reversible hydrogen electrode (RHE).
ERHE ¼ EAg/AgCl(3M KCl) þ 0.209 V þ 0.059 V  pH.
Battery tests were performed in Zn-air cell using directly grown
MnOx on carbon paper air cathode and polished Zn plate anode. Ti
mesh and hydrophobic carbon paper were placed next to air
cathode as current collector and waterproof backing layer. Area of
air cathode exposed to electrolyte and air is z0.79 cm2. Electrolyte
was injected into the cell after the assembly. Conductivity and pH of
electrolytes was measured by a conductivity and pH meter (Horiba
Scientific). Chloride-based electrolyte consisted of 5 M NH4Cl,
35 g L1 ZnCl2, and 1000 ppm thiourea. Conductivity and pH of as-
prepared chloride-based electrolyte was about 37.1 S m1 and 4.9,
respectively. NH4OH was used to adjust the pH of electrolyte to 7.
Upon pH adjustment, chloride-based electrolyte maintained
similar conductivity (z37.5 S m1) which is smaller than pH 14
alkaline electrolyte (z51.5 S m1). Alkaline electrolyte comprised
of 5 M KOH, 35 g L1 ZnCl2, and 1000 ppm thiourea. Thiourea was
added as brightening agent to produce fine zinc deposits during
charging which can mitigate the growth of Zn dendrite [11,27].
Polarization curves and Nyquist plots were obtained from galva-
nodynamic and electrochemical impedance spectroscopy (EIS)
measurements (potentiostat, Autolab PGSTAT302N). Cycling test
was performed using recurrent galvanostatic test (battery tester,
Maccor 4300).
Morphology and elemental analysis of the samples was inves-
tigated by scanning electron microscopy and energy dispersive X-
ray spectroscopy (FESEM, JEOL JSM-6700F). Crystal structure of the
samples was studied by X-ray diffractrometer (Bruker D8 Advance).
Gas identification during charging of Zn-air batteries was carried
out by gas chromatography mass spectrometry (GC-MS, Varian
GC3800 and MS4000). The battery was subjected to constant
voltage of 2.2 V for 48 h in a closed container that had been purged
by Ar gas. The collected gas in the container was then introduced to
the head of GC-MS column.
332 A. Sumboja et al. / Journal of Power Sources 332 (2016) 330e336
3. Results and discussion
Rotating disk linear sweep voltammetry (LSV) was employed to
assess kinetics of ORR and OER of MnOx catalyst in three different
types of electrolyte (i.e. NH4Cl, NH4Cl pH 7, or KOH). LSV curves
showing ORR activities of directly grown MnOx on carbon in 0.1 M
NH4Cl pH 7 and 0.1 M KOH are given in Fig. 1aeb. Onset potential of
MnOx catalyst for ORR measured at rotation speed of 1600 rpm
varies with pH of electrolyte, showing 0.92, 0.56, and 0.46 V in
alkaline, pH 7 chloride-based, and chloride-based electrolyte,
respectively (Supplementary Data Fig. S1). Despite the more
negative onset potential, MnOx catalyst in chloride-based electro-
lyte has similar diffusion limiting current density as that of MnOx in
alkaline electrolyte. However, current density of MnOx in neutral
electrolyte continue to increase with the potential which is asso-
ciated with the poor kinetics of MnOx in 0.1 M NH4Cl pH 7, leading
to a to mixed kinetics-diffusion limiting mechanism [28,29].
Humps in the current density were observed in the diffusion
limiting current region, especially at high rotating speed mea-
surements. This phenomenon is commonly observed in the litera-
ture which is attributed to the variation of the mass transport onto
the porous structure of electrocatalyst [30e32]. It is noteworthy
that as-synthesized MnOx is highly porous as shown from SEM
imaging (Supplementary Data Fig. S2) RDE cyclic voltammograms
further confirm the occurrence of ORR in alkaline and chloride-
based electrolytes. Unlike the featureless voltammograms ob-
tained in N2 environment (dotted curves in Fig. 1c), the
Fig. 1. Oxygen reduction polarization curve of MnOx on carbon at various rotation speeds in (a) 0.1 M NH4Cl pH 7 and (b) 0.1 M KOH. (c) RDE cyclic voltammograms of MnOx on
carbon at rotation speed of 1600 rpm in various electrolytes (dotted curve: N2 environment, solid curve: O2 environment). (d) Oxygen evolution polarization curves of MnOx on
carbon at rotation speed of 1600 rpm in various electrolytes.
voltammograms show apparent reduction current at potential
similar to LSV measurements in O2 environment (solid curves in
Fig. 1c), which indicate significant ORR activities in alkaline and
chloride-based electrolytes.
On the other hand, OER of MnOx catalyst in alkaline and
chloride-based electrolytes was observed to start around the same
onset potential (z1.60 V). However, in comparison to sharp in-
crease of current density between 1.6 and 1.7 V in alkaline elec-
trolyte, the slower increment of current density of MnOx in
chloride-based electrolyte suggests the sluggish OER kinetics of
MnOx catalyst in chloride-based electrolytes (Fig. 1d). Onset po-
tential for ORR and OER of MnOx on carbon in 0.1 M KOH are
comparable to other metal oxides-based bifunctional catalyst in
literature [23,32,33], while RDE studies for MnOx on carbon in
NH4Cl electrolyte has yet to be reported. Hence, ORR and OER ac-
tivity of MnOx on carbon depends on the pH of electrolyte, showing
the highest activity in alkaline electrolyte.
Catalytic activity of MnOx in chloride-based electrolyte with
pH ¼ 7 is better than its counterpart in the as-prepared chloride-
based electrolyte (e.g. without pH adjustment). Limited catalytic
activity of MnOx in neutral electrolyte can be attributed to the small
quantity of OH for catalytic reactions and low conductivity of
neutral electrolyte, leading to the low catalytic activity in neutral
electrolyte. Catalytic current of Ni/N-doped graphene in 0.5 M
Na2SO4 is reported to be 4% of its catalytic current in 0.1 M KOH due
to the low concentration of OH in Na2SO4. [34] Takashima et al.
[35] studied water oxidation with MnO2 catalyst in 0.5 M Na2SO4.
 A. Sumboja et al. / Journal of Power Sources 332 (2016) 330e336 333

OER activity of MnO2 was found to be pH-dependent, showing an
improved activity at pH > 9. Low OER activities in acidic and neutral
electrolyte are associated with the instability of Mn3þ at low pH
which functions as a precursor for O2 evolution [35]. Nevertheless,
catalytic activity of MnOx in chloride-based electrolyte is promising
as compared to MnO2 or carbon-based catalysts in other neutral
electrolytes [25,34]. Thus, it is of interest to explore its application
in Zn-air batteries.
Discharge and charge polarization curves of Zn-air batteries
with alkaline and pH 7 chloride-based electrolytes are given in
Fig. 2a. Low conductivity of chloride-based electrolyte and limited
catalytic activity of MnOx result in the large overpotential of Zn-air
batteries with chloride-based electrolyte, especially at high current
density measurements (Fig. 2a). Power densities extracted from the
discharge profile of both batteries are given in Fig. 2b, showing a
similar power density at low current density (10 mA cm2). The
maximum power density of the batteries with chloride-based
electrolyte was achieved at current density of 13.8 mA cm2,
giving a power density of 12.8 mA cm2. On the contrary, Zn-air
batteries with alkaline electrolyte were able to exhibit maximum
power density of 108 mA cm2 at 168 mA cm2 [20]. EIS mea-
surement also suggests the more resistive nature of the batteries
with pH 7 electrolyte as compared to the ones with alkaline elec-
trolyte (Supplementary Data Fig. S3). The high intercept at X axis
and huge diameter of semi-circle arc of Nyquist plot indicate the
large resistance of Zn-air batteries with pH 7 chloride-based elec-
trolyte [36].
Due to the limited performance of Zn-air batteries with
chloride-based electrolyte at high current density, galvanostatic
cycling test was performed at discharge/charge current of
1 mA cm2 for 4 h, per cycle (Fig. 2cef). The cells with alkaline
electrolyte show an initial discharge and charge voltage of 1.32 and
1.86 V, superior to the cells with pH 7 chloride-based electrolyte
(1.04 and 2.02 V). Despite the strong initial performance, the cells
with alkaline electrolyte continue to degrade over the time. At the
end of 200th cycle (z33 days), discharge and charge voltage

Fig. 2. Performance of Zn-air batteries with alkaline and pH 7 chloride-based electrolyte. (a) Galvanodynamic discharge and charge polarization curves. (b) Power density plots
extracted from galvanodymanic discharge curve. (c, d) Cycling stability. Discharge/charge curves during selected cycles in: (e) alkaline and (f) pH 7 chloride-based electrolyte.
334 A. Sumboja et al. / Journal of Power Sources 332 (2016) 330e336

Fig. 3. (a) Digital images of the used-alkaline and pH 7 chloride-based electrolytes after cycling test, suggesting the presence of carbon corrosion in alkaline electrolyte. (b, c) EDS
spectra and SEM image of residue collected from the used-alkaline electrolyte. Si signal is from the substrate during imaging.

changed to 1.20 and 2.1 V, giving 9.3 and 11.9% degradation,
respectively. The cells fail further after 41 days testing time (z245
cycles), showing discharge and charge voltage of 0.77 and 2.1 V
(Fig. 2e). On the contrary, the cells with pH 7 chloride-based elec-
trolyte show excellent stability for up to 540 continuous cycles
(z90 days). Voltage profile of the cells is almost constant during
the first 300 cycles (z50 days). At the end of 500th cycle, the cell
delivers discharge and charge voltage of 0.94 and 2.15 V which
correspond to 4.8 and 6.7% change, subsequently (Fig. 2f).
The improved stability of Zn-air batteries with pH 7 chloride-
based electrolyte is attributed to the reduced corrosion of carbon-
based air cathode and limited carbonation of electrolyte in
neutral electrolyte. Unlike alkaline electrolyte which changed to
brownish color, the pH 7 electrolyte maintained the same

Fig. 4. SEM images of MnOx on carbon paper air cathode: (a) before and (b) after cycling test in alkaline electrolyte, showing the presence of carbonate particles after cycling. (c)
XRD patterns of MnOx catalyst on carbon paper air cathode before and after cycling test in alkaline electrolyte. (d) GC-MS spectrum the collected gas during continues charging of
Zn-air batteries with chloride-based electrolyte at 2.2 V for 48 h. (e) The enlarged scale of Fig. 4d.
 A. Sumboja et al. / Journal of Power Sources 332 (2016) 330e336 335

Table 1
Cycling performance of rechargeable Zn-air batteries in literature.

Air Catalyst Electrolyte Number of Applied current/mA Cycling period per Change in discharge Change in charge Ref
cycle cm2 cycle/min voltage/% voltage/%

MnOx nanoparticles grown on carbon paper neutral 540 1 240 4.8 6.7
(this work)
MnO2 near- 104 1 mA and 0.5 mA 720 ~0 5 [11]
neutral
MnOx nanoparticles grown on carbon paper alkaline 500 15 15 10 8 [20]
MnO2 nanotubes/N-CNT alkaline 50 8 10 20 5 [36]
MnO2 nanorods/LaNiO3 nanoparticles/CNT alkaline 75 e e 1.4 4.8 [38]
MnO2 alkaline 4 15 1800 ~0 ~0 [39]
Ag nanoparticles grown on MnO2 nanorods alkaline 270 5 mA 20 ~0 ~0 [40]
Co3O4 nanoparticles grown on MnO2 alkaline 60 15 14 5 5 [41]
nanotubes
Co3O4 nanoparticles grown on carbon alkaline 55 20 60 7.6 ~0 [42]
nanofibers
Co3O4 grown on stainless steel alkaline 1200 17.6 10 ~0 ~0 [43]
CoO nanoparticles grown on N-CNT/NiFe alkaline 10 50 240 ~0 ~0 [6]
LDH
Co3O4 nanodisks alkaline 60 17.6 10 ~0 ~0 [44]
MnCo2O4 nanoparticles/CNT alkaline 64 10 720 4.9 4.9 [32]
NiCo2O4 nanowires alkaline 50 20 40 10 2.2 [45]
CoMn2O4 nanoparticles grown on N- alkaline 100 20 10 5.5 5.6 [46]
graphene
LaNiO3 nanoparticles/N-CNT alkaline 10 17.6 240 ~0 ~0 [47]
LaNiO3 macrospheres/N-CNT alkaline 75 17.6 10 1 4.5 [48]

transparent color after cycling test which indicates minimum car-
bon corrosion in Zn-air batteries with pH 7 chloride-based elec-
trolyte (Fig. 3a). Both electrolytes were centrifuged to collect the
residual particles. Almost no residue can be collected from the used
neutral electrolyte. Residue of the used alkaline electrolyte mainly
consists of C, Mn, Zn, and K, suggesting C and MnOx in the air
cathode were dissolved into the electrolyte after prolong cycling
test (Fig. 3bec).
Carbonation of alkaline electrolyte can be seen from the pres-
ence of carbonate particles on the used air cathode. Such big par-
ticles (up to 10 mm size) may block the access of O2, causing the
gradual passivation of air cathode (Fig. 4aeb, Supplementary Data
Fig. S4). XRD pattern of MnOx on carbon paper air cathode before
and after cycling test are given in Fig. 4c. XRD pattern of the air
cathode before the cycling test displays one sharp peak which is
related to the presence of carbon. The existence of amorphous
MnOx on the carbon paper has been confirmed by XPS study in our
previous work [20]. XRD pattern of the used air cathode exhibits a
complex set of distinct peaks, indicating the crystalline nature of
the carbonate particles. The peaks were found to match with hy-
droxy carbonate and carbonate of zinc and potassium. Given the
complex nature of the electrochemical process during the prolong
cycling test, it is possible for a mixture of carbonates to form.
The large-plate particle is most likely potassium carbonate as
the particles dissolved in cold water. The plate particles could not
be found on the used air cathode after immersion in cold water for
several hours (Supplementary Data Fig. S5). The growth of large
plate of potassium carbonate can be attributed to the leakage of
electrolyte. The carbon paper gradually lost its hydrophobicity
during prolong cycling test. The leaked electrolyte was able to reach
the outer side of air cathode and in contact directly with atmo-
sphere. As the electrolyte level in the cell continued to drop, the
growth of large plate of K2CO3 might proceed via solvent evapo-
ration process and humid environment might cause surface
roughening of the plate. Despite the removal of these plates from
the air cathode, the air cathode cannot be reused as most of carbon
and MnOx catalyst have been etched away during the cycling test.
Although chlorine evolution has lower overpotential than the
oxygen evolution, the formation of chlorine gas can be avoided by
using catalyst that has high selectivity towards OER. Manganese
oxide is a known material that has high selectivity towards oxygen
evolution in chloride-based solution [21,22,37]. In addition, OER is
favored at low charging current and high pH (pH  2) [17,21].
NH4OH in the electrolyte acts as a buffer to maintain the pH of the
electrolyte during the cycling test. The used pH 7 chloride-based
electrolyte has a pH of 6.5 which deviates slightly from its orig-
inal pH, but still with a proton concentration ([Hþ]) of 30,000 times
lower than that is required for chlorine evolution (pH  2). Thus,
the utilization of MnOx catalyst, NH4OH buffer, and low current
density during cycling test helps to suppress the chlorine genera-
tion in our battery. Furthermore, we have carried out gas chro-
matography mass spectrometry (GC-MS) to trace possible
formation of chlorine gas from chlorine evolution during contin-
uous charging of the Zn-air battery at 2.2 V for 48 h. We did not
detect any stable isotope of chlorine from the GC-MS spectra,
suggesting that there is no production of chlorine gas during
charging of Zn-air batteries with chloride-based electrolyte and
MnOx catalyst. The mass spectrum of the gas collected from Zn-air
batteries with chloride-based electrolyte and MnOx catalyst are
given in Fig. 4dee. Stable isotopes of chlorine (i.e. Cl-35 and Cl-37)
were not detected at mass-to-charge ratio (m/z) of 35, 37, 70, 72,
and 74. On the contrary, the highest signal (i.e. base peak) at m/z of
32 and the spectrum at m/z of 33 and 34 are related to the presence
of stable isotope of oxygen, signifying the presence of oxygen
evolution in our Zn-air battery.
Initial discharge and charge voltage of 1.04 and 2.02 V of our
batteries are better than Zn-air batteries with near-neutral elec-
trolytes [11,17], suggesting the advantage of further adjustment of
pH and conductivity of chloride-based electrolyte as well as the
directly grown MnOx catalyst on carbon paper air cathode. In
addition, voltage profile of Zn-air batteries with pH 7 electrolyte is
comparable to Zn-air batteries with alkaline electrolyte operated at
high applied currents [40,43,48]. For instance, Zn-air batteries with
Co3O4 catalyst grown on stainless steel reported initial discharge
and charge voltage of 0.98 and 2.0 V [43], while the batteries with
LaNiO3 supported N-CNT catalyst displayed a discharge and charge
voltage of z0.95 and 2.25 V [48]. Furthermore, stable discharge
and charge voltage of 1.0 and 2.1 V for up to 90 days cycling test
336 A. Sumboja et al. / Journal of Power Sources 332 (2016) 330e336
outperform stability of most rechargeable Zn-air batteries with
alkaline electrolyte [20,36,38,40,41,46,48,49] (Table 1) and Zn-air
batteries with pH 6 electrolyte and powder MnO2 catalyst [11],
indicating the advantage of neutral electrolyte and directly grown
catalyst on improving stability of Zn-air batteries.
4. Conclusions
Performance of rechargeable Zn-air batteries with pH 7
chloride-based electrolyte and directly grown MnOx catalyst on
carbon paper air cathode has been reported. Catalytic activity of
MnOx shows dependence of ORR and OER on the pH of electrolytes.
Low catalytic activity of MnOx in neutral electrolyte is attributed to
the small concentration of OH and poor conductivity of neutral
electrolyte. Despite that, batteries with pH 7 chloride-based elec-
trolyte show exceptional cycling stability as well as acceptable
charge and discharge voltage at low applied current. The improved
stability is attributed to the reduced carbon corrosion in air cathode
and less carbonation in the batteries with neutral electrolyte. Per-
formance of Zn-air batteries with neutral electrolyte at high applied
currents can be improved by incorporating more active catalysts
and tuning the properties of neutral electrolyte.
Acknowledgements
This research was supported by Advanced Energy Storage
Research Programme (IMRE/12-2P0503 and IMRE/12-2P0504),
Institute of Materials Research and Engineering of A*STAR,
Singapore. We thank Ms. Tan Sze Yu (IMRE) for GC-MS
characterization.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jpowsour.2016.09.142.
References
[1] Y. Li, H. Dai, Chem. Soc. Rev. 43 (2014) 5257e5275.
[2] J.S. Lee, S.T. Kim, R. Cao, N.S. Choi, M. Liu, K.T. Lee, J. Cho, Adv. Energy Mater. 1
(2011) 34e50.
[3] M. Xu, D. Ivey, Z. Xie, W. Qu, J. Power Sources 283 (2015) 358e371.
[4] P. Pei, K. Wang, Z. Ma, Appl. Energy 128 (2014) 315e324.
[5] P.C. Li, Y.J. Chien, C.C. Hu, J. Power Sources 313 (2016) 37e45.
[6] Y. Li, M. Gong, Y. Liang, J. Feng, J.E. Kim, H. Wang, G. Hong, B. Zhang, H. Dai,
Nat. Commun. 4 (2013) 1805.
[7] K. Nishio, S. Molla, T. Okugaki, S. Nakanishi, I. Nitta, Y. Kotani, J. Power Sources
278 (2015) 645e651.
[8] J.F. Parker, C.N. Chervin, E.S. Nelson, D.R. Rolison, J.W. Long, Energy Environ.
Sci. 7 (2014) 1117e1124.
[9] D.M. See, R.E. White, J. Chem. Eng. Data 42 (1997) 1266e1268.
[10] J. Jindra, J. Mrha, M. Musilov a, J. Appl. Electrochem 3 (1973) 297e301.
[11] F.W.T. Goh, Z. Liu, T.S.A. Hor, J. Zhang, X. Ge, Y. Zong, A. Yu, W. Khoo,
J. Electrochem. Soc. 161 (2014) A2080eA2086.
[12] K. Kinoshita, Electrochemical Oxygen Technology, vol. 30, John Wiley & Sons,
1992.
[13] M. De Koninck, P. Manseau, B. Marsan, J. Electroanal. Chem. 611 (2007)
67e79.
[14] P.N. Ross, H. Sokol, J. Electrochem. Soc. 131 (1984) 1742e1750.
[15] H. Arai, S. . Müller, O. Haas, J. Electrochem. Soc. 147 (2000) 3584e3591.
[16] Q. Zhou, C.M. Li, J. Li, X. Cui, D. Gervasio, J. Phys. Chem. C 111 (2007)
11216e11222.
[17] S. Amendola, M. Binder, P.J. Black, S. Sharp-Goldman, L. Johnson, M. Kunz,
M. Oster, T. Chciuk, R. Johnson, Electrically Rechargeable, Metal-air Battery
Systems and Methods, Eos Energy Storage, LLC (Edison, NJ, US), United States,
2013.
[18] W.M. Haynes, CRC Handbook of Chemistry and Physics, CRC press, 2014.
[19] R. Winand, Mod. Electroplat. 52 (2011) 285.
[20] A. Sumboja, X. Ge, F.W.T. Goh, B. Li, D. Geng, T.S.A. Hor, Y. Zong, Z. Liu,
ChemPlusChem 80 (2015) 1341e1346.
[21] S. Trasatti, Oxygen and Chlorine Evolution at Conductive Metallic Oxide An-
odes, 1981, p. 521.
[22] K. Izumiya, E. Akiyama, H. Habazaki, N. Kumagai, A. Kawashima, K. Hashimoto,
Electrochim. Acta 43 (1998) 3303e3312.
[23] Y. Meng, W. Song, H. Huang, Z. Ren, S.-Y. Chen, S.L. Suib, J. Am. Chem. Soc. 136
(2014) 11452e11464.
[24] P.C. Li, C.C. Hu, T.C. Lee, W.S. Chang, T.H. Wang, J. Power Sources 269 (2014)
88e97.
[25] I. Roche, K. Scott, J. Appl. Electrochem 39 (2009) 197e204.
[26] L. Zhang, C. Liu, L. Zhuang, W. Li, S. Zhou, J. Zhang, Biosens. Bioelectron. 24
(2009) 2825e2829.
[27] C. Loto, R. Loto, Int. J. Electrochem. Sci. 8 (2013) 12434e12450.
[28] G. Gotti, K. Fajerwerg, D. Evrard, P. Gros, Int. J. Electrochem. Sci. 8 (2013)
12643e12657.
[29] Z. Mo, S. Liao, Y. Zheng, Z. Fu, Carbon 50 (2012) 2620e2627.
[30] J. Wu, Z. Yang, Z. Wang, Q. Sun, R. Yang, Electrochem. Commun. 42 (2014)
46e49.
[31] J. Zhang, C. Guo, L. Zhang, C.M. Li, Chem. Commun. 49 (2013) 6334e6336.
[32] X. Ge, Y. Liu, F.W.T. Goh, T.S.A. Hor, Y. Zong, P. Xiao, Z. Zhang, S.H. Lim, B. Li,
X. Wang, Z. Liu, ACS Appl. Mater. Interfaces 6 (2014) 12684e12691.
[33] F. Cheng, Y. Su, J. Liang, Z. Tao, J. Chen, Chem. Mater. 22 (2009) 898e905.
[34] S. Chen, J. Duan, J. Ran, M. Jaroniec, S.Z. Qiao, Energy Environ. Sci. 6 (2013)
3693e3699.
[35] T. Takashima, K. Hashimoto, R. Nakamura, J. Am. Chem. Soc. 134 (2012)
1519e1527.
[36] Z. Chen, A. Yu, R. Ahmed, H. Wang, H. Li, Z. Chen, Electrochim. Acta 69 (2012)
295e300.
[37] K. Fujimura, T. Matsui, K. Izumiya, N. Kumagai, E. Akiyama, H. Habazaki,
A. Kawashima, K. Asami, K. Hashimoto, Mater. Sci. Eng. A 267 (1999) 254e259.
[38] H. Ma, B. Wang, RSC Adv. 4 (2014) 46084e46092.
[39] G. Toussaint, P. Stevens, L. Akrour, R. Rouget, F. Fourgeot, ECS Trans. 28 (2010)
25e34.
[40] F.W.T. Goh, Z. Liu, X. Ge, Y. Zong, G. Du, T.S.A. Hor, Electrochim. Acta 114
(2013) 598e604.
[41] G. Du, X. Liu, Y. Zong, T.S.A. Hor, A. Yu, Z. Liu, Nanoscale 5 (2013) 4657e4661.
[42] B. Li, X. Ge, F.W.T. Goh, T.S.A. Hor, D. Geng, G. Du, Z. Liu, J. Zhang, X. Liu,
Y. Zong, Nanoscale 7 (2015) 1830e1838.
[43] D.U. Lee, J.Y. Choi, K. Feng, H.W. Park, Z. Chen, Adv. Energy Mater. 4 (2014) n/
a-n/a.
[44] D.U. Lee, J. Scott, H.W. Park, S. Abureden, J.-Y. Choi, Z. Chen, Electrochem.
Commun. 43 (2014) 109e112.
[45] M. Prabu, K. Ketpang, S. Shanmugam, Nanoscale 6 (2014) 3173e3181.
[46] M. Prabu, P. Ramakrishnan, S. Shanmugam, Electrochem. Commun. 41 (2014)
59e63.
[47] D.U. Lee, H.W. Park, M.G. Park, V. Ismayilov, Z. Chen, ACS Appl. Mater. In-
terfaces 7 (2014) 902e910.
[48] Z. Chen, A. Yu, D. Higgins, H. Li, H. Wang, Z. Chen, Nano Lett. 12 (2012)
1946e1952.
[49] Y. Zhan, C. Xu, M. Lu, Z. Liu, J.Y. Lee, J. Mater. Chem. A 2 (2014) 16217e16223.