energies

Article
Low-Temperature Performance of Al-air Batteries
Yuxin Zuo 1 , Ying Yu 2, * , Chuncheng Zuo 2, *, Chuanlong Ning 2 , Hao Liu 2 , Zhiqing Gu 2 ,
Qianqian Cao 2 and Ciming Shen 2
1 College of Design, Jiaxing University, Jiaxing 314000, China; yuxinzuo@mail.zjxu.edu.cn
2 College of Mechanical and Electrical Engineering, Jiaxing University, Jiaxing 314000, China;
ningchuanlong@outlook.com (C.N.); hliu@mail.zjxu.edu.cn (H.L.); guzhiqing111@mail.zjxu.edu.cn (Z.G.);
qqcao@mail.zjxu.edu.cn (Q.C.); happyciming@outlook.com (C.S.)
* Correspondence: yingyu@mail.zjxu.edu.cn (Y.Y.); zuocc@mail.zjxu.edu.cn (C.Z.)




Received: 3 January 2019; Accepted: 12 February 2019; Published: 15 February 2019


Abstract: High demand for batteries with a wide operating temperature range is on the rise with the
development of wearable electronic devices, especially electric vehicles used in cold regions. Al–air
batteries for electric vehicles have triggered worldwide interest due to their excellent theoretical
energy density and safety. In this study, the low-temperature performance of Al–air batteries is
tested for the first time. The effects of temperature and electrolyte concentrations on the discharge
performance are then studied in detail. The discharge voltage is significantly influenced by the
temperature. The low temperature could significantly depress the hydrogen evolution reaction of Al
anodes. The Al–air batteries reached an extraordinary capacity of 2480 mAh/g, with 31 wt% KOH
electrolyte at −15 ◦ C. Moreover, the Al–air batteries at 0 ◦ C exhibited higher discharge voltage and
power densities than those at 15 and −15 ◦ C. This study provides an important reference for future
studies to improve low-temperature performance of Al–air batteries.

Keywords: al-air battery; low temperature; discharge performance

1. Introduction
Besides the rapid advancement of modern industrial technology, other factors, such as
environment friendliness, cleanliness, and being an alternative inexpensive energy source have become
the subject of research because of the limitations of traditional energy, i.e., fossil fuel exhaustion and
risk of climatic degeneration [1]. Metal–air batteries are one of the most promising candidates for
next-generation energy storage due to their high capacity and energy density. Al–air batteries have
driven the increasing concern due to their high specific energy density, low cost [2], and stability
in solid gel electrolyte [3] or the electrolyte with additives (such as ZnO/PEG di-acid inhibitor and
non-conductive oil) [4,5]. The application of these batteries has spread to remote communications,
railroad signaling, seismic telemetry, and power grids. Moreover, the high safety and long platform of
discharge make them a prominent power storage source for hybrid electric vehicles [6,7]. Although
significant progress has been achieved in enhancing the electrochemical performance of Al–air battery,
a critical issue that seriously restricts its future commercialization and practical application remains.
Batteries are sensitive to environmental conditions, especially to temperature. However, few studies
focus on low-temperature (LT) performance of Al–air batteries, which is of considerable importance
for the development of Al–air battery. For example, understanding the effects of winter operation for
electric vehicles is critical in cold regions, such as Switzerland, Canada, Northern USA, Northeast
China, and Russia.
Scientists have already realized that a broad application temperature range is a big challenge
for battery development. Numerous papers have addressed the problem of poor LT performance of

Energies 2019, 12, 612; doi:10.3390/en12040612 www.mdpi.com/journal/energies

Energies 2019, 12, 612 2 of 10

various kinds of batteries [8–13]. If the temperature falls to the subzero range, then the electrochemical
performance and stability of batteries can be dramatically reduced, depending on the battery chemistry
in comparison with those at room temperature. Ji et al. [14] have shown that the sluggish diffusion
process of ions at LT leads to the remarkable deterioration of electrochemical performance. For
vanadium redox flow batteries, a relatively low energy density is limited by the solubility of vanadium
ions in the sulfuric acid supporting electrolyte at LT [15]. The high capability and cycling stability
of Na-ion batteries are substantially reduced when temperature falls below 0 ◦ C [16]. Most studies
focused on the LT performance of Li-ion batteries, particularly for propelling electric vehicles [11,17–19].
Some studies suggest that discharge capacity and operating voltage are limited by the poor ionic
conductivity of electrolytes and low diffusivity of lithium ion within graphite anodes at LT. A study
reported that Li-ion batteries could only deliver 5% of its capacity at −40 ◦ C compared with that at
20 ◦ C [12,20]. Researchers focus on improving battery cycling stability and capacity at LT [14,21–28].
Al–air batteries exhibits evident advantages over Li-ion batteries. Al–air batteries are safe and cost
effective, and their raw materials are widely available. These advantages demonstrate that the Al–air
battery has the potential to be a backbone technology for the energy storage of electric vehicles in
the future. However, the LT performance of the Al–air battery has never been tested or investigated.
Therefore, studying the mechanisms of LT performance for the Al–air battery is crucial and challenging.
Based on the aforementioned reasons, the LT electrochemical performance for Al–air batteries
is comprehensively tested in this study. The following section presents a detailed fabrication of the
Al–air battery. In addition, the electrochemical performance is tested and discussed. The results could
provide suggestions for developing better-performing Al–air batteries.

2. Experiment

2.1. Materials
All materials in this study were of analytical grade and used without further treatment. Reagents
for the air cathode synthesis, including activated carbon, ether black, poly(vinylidene fluoride) (PVDF),
and Ni foam, were purchased from Shenyang Kejing. Catalysts, including MnO2 , La2 O3 , SrO, and
ZnO, were from Sinopharm Chemical Reagent. Organic solvent N-methyl pyrrolidone (NMP) was
provided by Shanghai Hushi Laboratorial Equipment Co., Ltd. Al foil and KOH (from Chinasun
Specialty Products Co., Ltd.) solution served as the metal anode and electrolyte, respectively.

2.2. Fabrication of Al-air Batteries

Air cathode was prepared according to the method used in our previous study [3], with conductive
carbon materials, catalysts, binder, and current collector. A mixture of activated carbon (70 g), ether
black (10 g), MnO2 (10 g), La2 O3 (8 g), and SrO (2 g) was milled together with PVDF (8 g) binder.
Thereafter, the solid blend in NMP dispersed, forming a 400 ml viscous paste, which was smeared
evenly on the surface of the Ni foam and dried for 24 h at ambient temperature. A 0.3 mm-thick
cathode plate was obtained by pressing it at 8 MPa.
All experiments comprised KOH and ZnO aqueous alkaline solutions in distilled water as
an electrolyte. ZnO additive in alkaline solutions was used as a corrosion inhibitor [3,5,29–33].
The concentrations of KOH and ZnO were α and (α/30) wt% respectively. Al foil with 20 µm thickness
was used as the metal anode and cut into 6 cm × 6 cm, and the reaction area is a circle with a diameter
of 4 cm and weight of 0.067 g. The Al–air batteries were finally assembled, as shown in Figure 1.
The distance between the aluminum and air electrode is 6 cm.
Energies 2019, 12, 612 3 of 10
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Figure
Figure 1.
1. Schematic
Schematic illustration
illustration of
of the
the assembled
assembled Al–air
Al–air battery.

2.3. Electrochemical
2.3. Electrochemical Tests
Tests
Conductivity is
Conductivity is one
one of of the
the most
most important
important factors
factors that
that affect
affect electrochemical
electrochemical performance.
performance.
Different contents
Different contents of
of KOH
KOH pellets
pellets were
were added
added intointo distilled
distilled water,
water, and
and the
the conductivities were
conductivities were
measured each time at different temperatures. A pair of Pt electrode was immersed
measured each time at different temperatures. A pair of Pt electrode was immersed in the electrolyte in the electrolyte
solution to
solution tomeasure
measure thetheconductivity withwith
conductivity a Mettler ToledoToledo
a Mettler FE30 conductivity testing system.
FE30 conductivity testingDischarge
system.
characteristics of the assembled Al-air batteries were measured using a LAND
Discharge characteristics of the assembled Al-air batteries were measured using a LAND battery battery testing system
at room, zero, and subzero temperatures. Once the cell was assembled, a 5 min
testing system at room, zero, and subzero temperatures. Once the cell was assembled, a 5 min period period was left to
allowleft
was good to impregnation of electrodes to
allow good impregnation of stabilize
electrodes thetoopen circuitthe
stabilize potential. To characterize
open circuit potential. the
To
self-discharge behavior, Tafel extrapolation was performed using an electrochemical
characterize the self-discharge behavior, Tafel extrapolation was performed using an electrochemical workstation
RST5000 in the
workstation conventional
RST5000 in the three-electrode cell. A Platinum
conventional three-electrode wire
cell. A was used aswire
Platinum the counter
was used electrode
as the
and mercury/mercuric
counter oxide (Hg/HgO) was
electrode and mercury/mercuric oxideused as the reference
(Hg/HgO) was used electrode. The working
as the reference electrode
electrode. The
was the Al anode. After the Al anodes were immersed in electrolyte for 20 min
working electrode was the Al anode. After the Al anodes were immersed in electrolyte for 20 min toto allow for potential
stabilization;
allow potentiodynamic
for potential stabilization;polarization was conducted
potentiodynamic polarizationat awas
1 mV/s scan rate.
conducted at a 1The
mV/svoltage scan
scan rate.
range of the anodic polarizing curve was − 0.5 to 0.5 V vs. open circuit potential.
The voltage scan range of the anodic polarizing curve was −0.5 to 0.5 V vs. open circuit potential.

3. Results and Discussion

3. Results and Discussion
3.1. Ionic Conductivity
3.1. Ionic Conductivity
Figure 2 shows the conditions of KOH solution (with α = 20, 30, and 40 concentration), which was
kept Figure 2 shows
frozen for −25
24 h atthe ◦ C. Distilled
conditions of KOH
water solution (with
was also  for
frozen = 20, 30, and 40purposes.
comparative concentration),
As shownwhich
in
was kept frozen
the figure, the KOH forsolution
24 h at at
−25a low
°C. Distilled water(20
concentration was alsowas
wt%) frozen forand
frozen, comparative purposes.
the solution As
still flowed
shown
evenly in at the figure, LT
extremely theat
KOH
highsolution at a low This
concentrations. concentration (20 wt%) well
finding illustrates was that
frozen,
KOHandsolution
the solution
with
still flowed evenly
concentration higheratthan
extremely
20 wt%LT at high
could concentrations.
be adopted in Al–airThis finding
battery at LT.illustrates well that KOH
solution with
Figure 3 concentration higher than 20
displays the conductivity of wt% could be
electrolyte adopted
solution in Al–airKOH
(including battery at ZnO)
and LT. in terms
of the mass fraction of KOH and temperature. The conductivity decreases further with decreasing
temperature. Conductivity decreases with increasing KOH content after the peak because of increased
viscosity and restricted ion mobility [34–36]. The highest conductivity of around 560 mS cm−1 is
observed at KOH content 31.5 at 15 ◦ C. Fairly high conductivity of 230 mS cm−1 with content 28 wt%
is evident when the temperature is lowered to −15◦ C. The KOH content is fixed at 25 and 31 wt%
(α = 25 and 31) in the following research.
3.1. Ionic Conductivity

Figure 2 shows the conditions of KOH solution (with  = 20, 30, and 40 concentration), which
was kept frozen for 24 h at −25 °C. Distilled water was also frozen for comparative purposes. As
shown in the figure, the KOH solution at a low concentration (20 wt%) was frozen, and the solution
Energies 2019, 12, 612 4 of 10
still flowed evenly at extremely LT at high concentrations. This finding illustrates well that KOH
solution with concentration higher than 20 wt% could be adopted in Al–air battery at LT.

Energies 2019, 12, x FOR PEER REVIEW 4 of 10

Figure 2. Photographs of KOH at different concentrations after being frozen for 24 h at −25 °C. Pure
water on the left is used for comparison.

Figure 3 displays the conductivity of electrolyte solution (including KOH and ZnO) in terms of
the mass fraction of KOH and temperature. The conductivity decreases further with decreasing
temperature. Conductivity decreases with increasing KOH content after the peak because of
increased viscosity and restricted ion mobility [34–36]. The highest conductivity of around 560 mS
cm−1 is observed at KOH content 31.5 at 15 °C. Fairly high conductivity of 230 mS cm−1 with content
28 wt% is evident when the temperature is lowered to −15°C. The KOH content is fixed◦ at 25 and 31
Figure 2. Photographs of KOH at different concentrations after being frozen for 24 h at −25 C. Pure
wt% (  = 25 and 31) in the following research.
water on the left is used for comparison.

Figure 3. Conductivity curve of KOH at different concentrations and temperatures.

Figure 3. Conductivity curve of KOH at different concentrations and temperatures.
3.2. Electrochemical Characterization
3.2. Electrochemical Characterization
Figure 4 shows the discharge behaviors of the Al–air battery using 25 wt% KOH electrolyte
Figure
solution 4 shows
at constant the discharge
current densities behaviors
of 0.5 mA cm of −
the Al–air
2 (a) and 1.0battery
mA cm using
−2 (b).25 The
wt%result
KOHshowselectrolyte
that
solution
the Al–airat constant
battery at 0current densities
◦ C exhibits of 0.5 mA voltage
an open-circuit cm (a)of
−2 and
1.411.0
V,mA
whichcmis (b).
−2 Thethan
higher result
thatshows that
of other
the Al–air battery at 0 °C exhibits an open-circuit voltage of 1.41 V, which
temperatures, whereas the lowest open-circuit and platform voltage appeared at −15 C. The cathodeis higher than
◦ that of other
temperatures,
reaction wouldwhereas the lowest
be affected by theopen-circuit and platform
diffusion coefficient voltage appeared
of oxygen. According at −15 °C. The cathode
to Arrhenius-type
reaction would be affected by the diffusion coefficient of oxygen.
equation [37], the gas diffusion coefficient decreases with temperature. However, proper According to Arrhenius-type
LT would
inhibit the hydrogen evolution of Al anode. Additionally, the discharge time of the Al–airLTbattery
equation [37], the gas diffusion coefficient decreases with temperature. However, proper would
atinhibit theishydrogen
−15 ◦ C unexpectedly evolution
up to of
25Al h. anode. Additionally,
The discharge time isthe discharge
related to thetime of the Al–air
utilization battery
of Al foil. Theat
−15 °C is unexpectedly up to 25 h. The discharge ◦ time is related to the
hydrogen generation was barely observed at −15 C, thereby indicating that the LT improves the utilization of Al foil. The
stability of the Al–air battery and suppresses the parasitic reaction. At a discharge current density the
hydrogen generation was barely observed at −15 °C, thereby indicating that the LT improves of
stability
0.5 mA cmof−2the Al–air4a),
(Figure battery and suppresses
the Al–air the parasitic
battery achieves reaction.
a capacity of 116At a discharge
mAh/g at 25 ◦current
C, which density
is onlyof
0.5 mA
4.03% of cm
−2 (Figure 4a), the Al–air battery achieves a capacity of 116 mAh/g at 25 °C, which is only
aluminum’s theoretical capacity (2980 mAh/g [38]), and the gravimetric energy density is
4.03% of aluminum’s ◦
142 Wh/g. At −15 C, Al–air theoretical capacity
battery (2980
exhibited mAh/g
a much [38]), and
superior the gravimetric
capacity of 2343 mAh/g energy density
at the sameis
142 Wh/g.
current At −15
density, °C, is
which Al–air
78.68%battery
of theexhibited
theoreticala much
value.superior capacity energy
The gravimetric of 2343density
mAh/g is at2480
the same
Wh
current density, which is 78.68% of the theoretical value. The gravimetric
g−1 . Compared with the current density 0.5 mA cm−2 case, the capacity increases by 1.12, 1.84, energy density is 2480andWh
g . Compared with the current density 0.5 mA cm case, the capacity increases by 1.12, 1.84, and
−1 −2
2.175 folds at −15 ◦ C, 0 ◦ C, and 15 ◦ C, respectively, at 1.0 mA cm−2 (Figure 4b). The conductivity of
2.175 folds at −15 °C, 0 °C, and 15 °C, respectively, at 1.0 mA cm−2 (Figure 4b). The conductivity of
electrolyte is essential for the discharge performance. LT results in the reduction OH− activity, which
electrolyte is essential for the discharge performance. LT results in the reduction OH- activity, which
also improves the oxygen reduction reactions. The extraordinary capacity is mainly due to the effect of
also improves the oxygen reduction reactions. The extraordinary capacity is mainly due to the effect
LT on the anodic reaction.
of LT on the anodic reaction.
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Energies 2019, 12, 612 5 of 10

Figure4.4. Discharging voltage

Figure voltageprofiles
profileswith
witha constant
a constantcurrent density
current of 0.5
density of mA mA−2:cm
0.5 cm −2and
(a) : (a)1.0and
mA
Figure 4. Discharging voltage profiles with a constant current density of 0.5 mA cm−2: (a) and 1.0 mA
cmmA
1.0 −2; (b) − 2
cmby ;using
(b) by25 wt%25
using KOH.
wt% KOH.
cm−2; (b) by using 25 wt% KOH.

The
The discharging
The discharging performances
dischargingperformances
are
performances are
also
are also
tested
also tested
using
tested using
a higher
higherconcentration
using aa higher concentration(31
concentration
(31 wt%)
(31wt%) KOH
wt%)KOH KOH
electrolyte solution with constant current densities of 0.5 and 1.0 mA cm −2−2. With increasing electrolyte
electrolyte solution with constant current densities of 0.5 and 1.0 mA cm . With increasing
electrolyte solution with constant current densities of 0.5 and 1.0 mA cm . With increasing electrolyte
−2 electrolyte
concentration,
concentration,
concentration, the
theAl–air
Al–air
the battery
Al–airbattery achieves
battery achieveshigh
achieves highdischarge
high dischargevoltage
discharge voltagebut
voltage butlow
but lowcapacities,
low asasshown
capacities,as
capacities, shown
shown ininin
Figure
Figure 5. 5.
Figure When
5.Whenthe the
When electrolyte concentration
theelectrolyte
electrolyte is high,is
concentration
concentration isthe aluminum
high,
high, oxidationoxidation
the aluminum
the aluminum rate increases.
oxidation Therefore,
rateincreases.
rate increases.
the batteries
Therefore, exhibit
the high
batteries discharge
exhibit highvoltage, short
discharge discharge
voltage, time,
short and
discharge low capacities.
time, and
Therefore, the batteries exhibit high discharge voltage, short discharge time, and low capacities.low capacities.

Figure 5. Cont.
 Energies 2019, 12, 612 6 of 10
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Figure 5. Discharging voltage profiles with a constant current density of 0.5 mA cm−2: (a) and 1.0 mA
cm−2; (b) by using 31 wt% KOH.

The potentiodynamic polarization at different temperatures was measured using a three-

electrode system. Figure 6 and Table 1 respectively present the Tafel curves and corresponding
corrosion parameters of Al anodes in 25 wt% KOH (Figure 6a) and 31−2wt% KOH (Figure 6b)
Figure 5. Discharging voltage profiles with a constant current density of 0.5 mA cm : (a) and 1.0 mA
Figure
electrolyte 5. Discharging voltageof
profiles with a constant current(density
Ecorr ) ofand
0.5 the
mA cm : (a) andcurrent
1.0 mA density
−2
cm−solutions.
2 ; (b) The
by using 31 values
wt% KOH. the corrosion potential corrosion
cm−2; (b) by using 31 wt% KOH.
( I corr ) are
Thecalculated from polarization
potentiodynamic the Tafel plots. The corrosion
at different inhibition
temperatures efficiency
was measured using aisthree-electrode
calculated by the
The potentiodynamic polarization at different temperatures was measured using a three-
following
system.formula
Figure 6asand
used in Reference
Table [39–41].
1 respectively present the Tafel curves and corresponding corrosion
electrode system.
parameters Figure
of Al anodes 6 and
in 25 wt%Table 1 respectively
KOH (Figure 6a) and present
31 wt% KOH the Tafel curves
(Figure and corresponding
6b) electrolyte solutions.
corrosion parameters of potential
Al anodes in )25 wt% KOH (Figure 6a)density
and 31(I wt% KOH (Figure 6b)
The values of the corrosion (Ecorr I corr − I corr (inh )
and the corrosion current corr ) are calculated from
electrolyte
the solutions.
Tafel plots. The values
The corrosion ofthe
inhibition =
%corrosion
efficiency potential 
(E
is calculated 100by),the
corr andfollowing
the corrosion current
formula density
as used in
Reference
( I corr ) are[39–41].
I corr
calculated from the Tafel plots. The corrosion inhibition efficiency is calculated by the
Icorr − Icorr(inh)
following formula as used in Reference η% =[39–41]. × 100,
I Icorr
where the corr and I corr ( inh ) are the corrosion current densities at 15 °C and other temperatures,
where the Icorr and Icorr(inh) are the corrosion current densities at 15 ◦ C and other temperatures,
respectively. Based on the Tafel plot results,Ithe corr − I corr (inh ) current density of Al–air batteries◦at 15°C
corrosion
respectively. Based on the Tafel plot results,  % = the corrosion current 100 , density of Al–air batteries at 15 C
is clearly much larger than that of 0 or −15 ◦°C, and
I the
is clearly much larger than that of 0 or −15 C, andcorrthe corrosion potential corrosion potential shifts,
shifts, implying
implying that itthat
is it is
lessless
corrosion resistant and possesses the largest self-corrosion rate than that
corrosion resistant and possesses the largest self-corrosion rate than that of others. As illustrated of others. As illustrated
in Table
inwhere1, the
Table the inhibition
1, theI corr and efficiencies
inhibition I corr are
( inh ) are are
efficiencies much
the much
corrosionhigh
high atatLT.
current LT. The largest
densities
The largest 15inhibition
atinhibition
°C and efficiency
other
efficiency is obtained
temperatures,
is obtained
at −15 −°C. ◦
15 This finding
atrespectively.
C. This Based onfurther
finding further
the Tafel confirms
confirms the the
plot results, discharged
discharged
corrosionbehaviorsbehaviors in in
current density Figures
Figures 4 and
of Al–air4 batteries
and
5. The5. LT
The LT can
can
at 15°C
significantly
significantly prevent
is clearly prevent
much larger the corrosion
the corrosion of aluminum
than that of 0 aluminum anodes
or −15 °C, andanodes in KOH electrolyte
in KOH potential
the corrosion electrolytesolution.
solution.
shifts, implying that it is
less corrosion resistant and possesses the largest self-corrosion rate than that of others. As illustrated
in Table 1, the inhibition efficiencies are much high at LT. The largest inhibition efficiency is obtained
at −15 °C. This finding further confirms the discharged behaviors in Figures 4 and 5. The LT can
significantly prevent the corrosion of aluminum anodes in KOH electrolyte solution.

Figure 6. Cont.
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Figure
Figure 6. 6. Potentiodynamicpolarization
Potentiodynamic polarization curves
curvesfor
forAlAlanodes
anodesmeasured
measuredin 25
inwt% KOH:
25 wt% (a) and
KOH: (a)31and 31
wt%wt% KOH;
KOH; (b)(b)atatdifferent
differenttemperatures.
temperatures.

Table 1. Corrosion parameters of Al anodes in KOH electrolyte at different temperatures.

Table 1. Corrosion parameters of Al anodes in KOH electrolyte at different temperatures.
KOH Content Temperature (◦ C) −Ecorr (V vs. Hg/HgO) Icorr (mA/cm2 ) η%
KOH −15 −1.490 0.232 84.33
25 wt% Temperature
0 (℃) −Ecorr (V−vs. Hg/HgO)
1.480 Icorr0.695 %
(mA/cm2) 53.02
Content 15 −1.471 1.479 –
−15 −1.487 0.448 44.54
−15 −1.490 0.232 84.33
31 wt% 0 −1.479 0.534 33.86
25 wt% 015 − 1.466
−1.480 0.807
0.695 –
53.02
15 −1.471 1.479 --
For further evaluation of the impacts of ambient temperature on Al–air battery, their
−15 −1.487 0.448 44.54
current–voltage/current–power curves in 25 wt% and 31 wt% KOH are shown in Figure 7a,b,
respectively.31The
wt%voltages ranged 0between 1550 and 350−1.479 0.534
mV, with an applied discharge 33.86
current density
− 2
in the range of 0.5–170 mA cm . With increasing current density, the discharge voltage decreased
15 −1.466 0.807 --
accordingly. The batteries at 0 ◦ C showed higher power density than that of others. The Al–air batteries
with 25 wt% KOH electrolyte reached the peak value of 101.14 ± 2.8 mW cm−2 (0 ◦ C) at 130 mA cm−2 ,
For further evaluation of the impacts of ambient temperature on Al–air battery, their current–
which is higher than that of 92.17 ± 2.6 mW cm−2 (15 ◦ C) and 80.21± 2.8 mW cm−2 (−15 ◦ C), as
voltage/current–power curves in 25 wt% and 31 wt% KOH are shown in Figure 7a,b, respectively.
depicted in Figure 7a. For cases of high electrolyte solution concentrations (31 wt%), the discharge
Thevoltages
voltages ranged between 1550 and
and power densities increase, as 350 mV,inwith
plotted Figurean7b.applied discharge
The maximum current
power density
densities reachin the
range
104 ±of 2.9
0.5–170
mW cmmA −2 (0cm◦ C) .atWith
−2
130 mA increasing
cm−2 , whichcurrent
is moredensity, the± discharge
than 95.55 2.7 mW cm−voltage
2 (15 ◦ C)decreased
and
accordingly.
84.37± 2.6 mWThe cm −
batteries
2 ◦
(−15 atC).0 These
°C showed higher
data provide power
rather density
surprising than thereby
results, that ofsuggesting
others. The thatAl–air
batteries withLT
the proper 25improves
wt% KOH theelectrolyte
power densityreached the battery.
of Al–air peak value of 101.14
Although the LT± environment
2.8 mW cm−2lowered
(0 °C) at 130
mAthe
cmelectrical
−2, whichconductivity
is higher than of electrolyte solution,
that of 92.17 LT repressed
± 2.6 mW cm−2 (15the
°C)hydrogen
and 80.21± evolution
2.8 mWreaction
cm−2 (−15and°C), as
promoted oxygen reduction reactions to a certain degree.
depicted in Figure 7a. For cases of high electrolyte solution concentrations (31 wt%), the discharge
voltages and power densities increase, as plotted in Figure 7b. The maximum power densities reach
104 ± 2.9 mW cm−2 (0 °C) at 130 mA cm−2, which is more than 95.55 ± 2.7 mW cm−2 (15 °C) and 84.37±
2.6 mW cm−2 (−15 °C). These data provide rather surprising results, thereby suggesting that the proper
LT improves the power density of Al–air battery. Although the LT environment lowered the electrical
conductivity of electrolyte solution, LT repressed the hydrogen evolution reaction and promoted
oxygen reduction reactions to a certain degree.
Energies 2019, 12, 612 8 of 10
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Figure
Figure 7. Discharging
7. Discharging voltageand
voltage andpower
powerdensity
density profiles
profiles versus
versuscurrent
currentdensity
densitywith
with25 25
wt%: (a) and
wt%: (a) and
31 wt%; (b) KOH electrolyte solutions.
31 wt%; (b) KOH electrolyte solutions.

4. Conclusions
4. Conclusions
Measurements
Measurements forfor
LTLT electrochemical
electrochemical performanceofof
performance Al–airbatteries
Al–air batteriesare
arereported
reportedfor
forthe
thefirst
firsttime.
Thetime. The combination
combination effects of temperature
effects of temperature and electrolyte
and electrolyte concentrations
concentrations on electrochemical
on electrochemical performance
are performance are discussed.
discussed. Different Differentare
temperatures temperatures
included for arecomparison.
included for Thecomparison.
LT has a The LT has effect
significant a
significant effect on the discharge performance. In the tests of constant current discharge, the capacities
on the discharge performance. In the tests of constant current discharge, the capacities of Al–air
of Al–air batteries can reach 2343 mAh/g with 25 wt% KOH electrolyte and 2480 mAh/g with 31 wt%
batteries can reach 2343 mAh/g with 25 wt% KOH electrolyte and 2480 mAh/g with 31 wt% KOH
KOH electrolyte at −15 °C. The corrosion experiments of Al anodes further demonstrate that the LT
electrolyte at −15 ◦ C. The corrosion experiments of Al anodes further demonstrate that the LT could
could effectively decrease the hydrogen evolution reaction. Surprisingly, the Al–air batteries ◦at 0 °C
effectively decrease
exhibit high the hydrogen
discharge voltage and evolution reaction.
power densities. TheSurprisingly,
peak value ofthe Al–air
power batteries
densities at 0at
°C0 reaches
C exhibit
high101.14
discharge voltage ◦
± 2.8 mW cm−2and power
(25 wt% KOH)densities.
and 104The peak
± 2.9 mWvalue of power
cm−2 (31 wt% KOH)densities
at 130atmA
0 cmC reaches
−2, which101.14
is
± 2.8 mW cm −2 (25 wt% KOH) and 104 ± 2.9 mW cm−2 (31 wt% KOH) at 130 mA cm−2 , which is
higher than that of −15 °C and 15 °C. Therefore, the proper LT could improve the performance of Al–
higher of −
than thatThis
air batteries. 15 ◦ Cresult
novel
◦ C. Therefore, the proper LT could improve the performance of
and is15crucial to studies focusing on power sources for wide temperature
Al–air batteries.
ranges. FurtherThis novel
studies onresult is crucial toofstudies
the improvement focusing battery
LT of metal–air on power sources for wide temperature
are needed.
ranges. Further studies on the improvement of LT of metal–air battery are needed.
Author Contributions: Conceptualization, Y.Z., Y.Y. and C.Z.; writing—original draft preparation, Y.Z. and Y.Y.;
writing—review and editing, C.N., H.L., Z.G., and C.S.; supervision, C.Z. and Q.C.
Author Contributions: Conceptualization, Y.Z., Y.Y. and C.Z.; writing—original draft preparation, Y.Z. and Y.Y.;
writing—review
Funding: Thisand editing,
research wasC.N., H.L.,by
funded Z.G.
theand C.S.; supervision,
National C.Z.Foundation
Natural Science and Q.C. of China (grant number
51775242 and 11802102), and the Zhejiang Provincial Natural Science Foundation (grant number LY19A020006
Funding: This research was funded by the National Natural Science Foundation of China (grant number
and LQ19E020003).
51775242 and 11802102), and the Zhejiang Provincial Natural Science Foundation (grant number LY19A020006
and Conflicts
LQ19E020003).
of Interest: The authors declare no conflict of interest.
Conflicts of Interest: The authors declare no conflict of interest.
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