Journal of Power Sources 592 (2024) 233923

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Journal of Power Sources

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

Electrode/electrolyte interface adjustment through adding mannitol into

the solution to improve the re-discharge performance of alkaline
Al-air batteries
Xuyang Wang a, Huihui Luo a, Tao Liu a, Lili Zhang b, Zigeng Liu c, Luxia Bu d, **, Wei Wang a, *
a
School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072, China
b
Science and Technology on Power Sources Laboratory, Tianjin Institute of Power Sources, Tianjin, 300384, China
c
Heraeus Battery Technology GmbH, Reinhard-Heraeus-Ring 29, 63801, Kleinostheim, Germany
d
Department of Applied Chemistry, College of Basic Science, Tianjin: Agricultural-University, Tianjin, 300392, China

H I G H L I G H T S

• Mannitol additive inhibits open-circuit corrosion of aluminum electrodes.

• Mannitol promotes re-discharge performance for Al-air batteries.
• Additives boost Al-Air battery applications.
• Electrode/electrolyte interface adjustment through adding mannitol.

A R T I C L E I N F O A B S T R A C T

Keywords: As a high-power battery system, Al-air batteries exhibit a wide range of potential applications. However, Al-air
Al− air battery batteries are susceptible to significant open-circuit corrosion of the aluminum electrodes when removed from the
Aluminum electrode electrolyte during standby, resulting in the formation of a dense film of corrosion products on the aluminum
Re-discharge
electrode surface. This, in turn, impedes the re-discharge performance of Al-air batteries. Based on an electrode/
Mannitol
Interface
electrolyte interface adjustment strategy, mannitol is used as the additive to be added into 4 M KOH solution to
improve re-discharge performance. Experimental analyses and theoretical calculations reveal that the inclusion
of mannitol enhances the re-discharge performance of Al-air batteries through a combination of hydrogen
bonding and adsorption. Importantly, it is noted that mannitol has minimal impact on the battery power density.
The reason for the improvement is explained reasonably by a proposed mechanism. These findings offer valuable
insights for the development of Al-air batteries with high performance.

1. Introduction
The demand for energy storage devices with high energy density and
safety has greatly increased due to the energy crisis and environmental
pollution problems [1,2]. Batteries have received a lot of attentions as
clean energy storage devices, and significant progresses have been made
in the field [3,4]. Aqueous metal-air batteries have attracted consider­
able attention and research efforts due to their safety and high energy
density [5,6]. Among metal-air batteries, aluminum-air batteries possess
a promising potential for large-scale energy storage applications due to
their low cost and high energy density (Al: 8100 Wh/kg) [6].
Typically, Al-air batteries comprise three key components: a pure
aluminum electrode as the negative electrode, an alkaline electrolyte
(such as KOH or NaOH in 4 M concentrations), and an air electrode as
the positive electrode [7,8]. Nevertheless, the aluminum anode presents
an issue of self-corrosion, involving hydrogen evolution in frequently
employed alkaline electrolytes. This phenomenon results in a reduction
in the energy conversion efficiency of Al-Air Batteries. To address this
concern, several modifications have been proposed, including alloying
the aluminum electrode [9], adding corrosion inhibitors into the

* Corresponding author.
** Corresponding author.
E-mail address: wangweipaper@tju.edu.cn (W. Wang).

https://doi.org/10.1016/j.jpowsour.2023.233923
Received 6 September 2023; Received in revised form 22 November 2023; Accepted 2 December 2023
Available online 14 December 2023
0378-7753/© 2023 Elsevier B.V. All rights reserved.
X. Wang et al.
electrolyte [10–12], utilizing gel electrolytes [13], and draining the
electrolyte after shutdown [14]. These modifications have been proven
effective in mitigating the corrosion and enhancing the overall perfor­
mance of aluminum-air batteries.
Alloying is achieved by introducing additional elements. The over­
potential for hydrogen precipitation can be increased by the incorpo­
ration of Zn, while the electrochemical activity can be augmented by
introducing In and Sn through the dissolution-redeposition mechanism.
Furthermore, the impact of impurity elements can be mitigated by the
addition of Mn [15,16]. Another approach involves incorporating suit­
able corrosion inhibitors into the electrolyte to minimize the corrosion
during the discharge process. Researches on inorganic corrosion in­
hibitors, such as ZnO [17] and SnO2− 3 , as well as organic corrosion in­
hibitors like CTAB [18], polyvinyl alcohol [19], benzoic acid [20], and
8-aminoquinoline [21], have been reported. Additionally, optimizing
the ratio of organic and inorganic corrosion inhibitors has been explored
to achieve improved corrosion inhibition effect [30,44].
Draining the electrolyte after shutdown greatly minimize the con­
sumption of the aluminum electrode caused by the corrosive. But a
considerable amount of residual electrolyte remains on the surface of the
aluminum electrode after draining the electrolyte [40,41], leading to the
formation of a thick and dense aluminum hydroxide film on the surface.
The thick and dense aluminum hydroxide film poses challenges when
restarting the battery after the shutdown/standby cycle. For instance, at
least 100 min was needed for the discharge current to get up little by
little to the initial discharge current density in a 4 M KOH solution after
restart the batteries [33]. Brandon J. Hopkins et al. addressed the issue
of passivation film by displacing the electrolyte with oil after discharge
[14]. However, the incorporation of oil storage in their device inevitably
led to an increase in device size.
As mannitol is cost-effective, non-toxic, and possesses a substantial
number of hydroxyl groups. Based on an electrode/electrolyte interface
adjustment strategy, we introduce mannitol as the additive into the
electrolyte, 4 M KOH solution, to improve the re-discharge performance
of Al-air batteries through reconstructing the adsorptive structure and
the solvent structure near the surface of the aluminum electrode.
Experimental analyses and theoretical calculations indicate that
mannitol facilitates the formation of a much stronger hydrogen bond
between the H2O molecule and the mannitol molecule, altering the
solvent structure near the surface and greatly suppress the diffusion of
the H2O molecules toward the surface during the corrosive reaction
process. Furthermore, the mannitol molecules strongly adsorb on the
surface and therefore totally change the interface structure, tremen­
dously declining the amount of H2O on the surface after removing the
electrolyte from the electrode. All of these lead to the formation of a
much thinner corrosive product film and the film is full of cracks causing
by imbedding mannitol molecules into the film, effectively improving
the re-discharge performance of the aluminum electrode. Finally, a
mechanism was proposed. (To elucidate the experimental concepts and
procedures comprehensively, we have meticulously organized and
summarized the pertinent information in Fig. S8.)
2. Experimental details
2.1. Materials and chemicals
In this work, the home-made aluminum alloy was used for electro­
chemical measurements and its components (wt.%) are as follows: Si
0.33, Cl 0.18, Fe 0.16, Na 0.13 and Al balance. Before each test,
Aluminum alloys were sanded to a smooth surface using 400–2000 grit
sandpaper to remove corrosion products, degreased with ethanol, rinsed
with deionized water and air dried. The electrodes were encapsulated
with hot-melt adhesive (Ningbo Deli Co, Ltd) so that the discharge area
was 4 cm2 (2 cm*2 cm). The blank electrolyte solutions used were 4.0 M
KOH (additive-free), prepared by dissolving KOH flakes (ACS, Shanghai
Titan Scientific Co., Ltd.) in deionized water. Mannitol was purchased
2
Journal of Power Sources 592 (2024) 233923
from Shanghai Aladdin Biochemical Technology Co., Ltd. The structure
of Mannitol was shown in Fig. S1.
2.2. Re-discharge measurement of the Al-air battery
The Al-air battery was assembled with an aluminum alloy plate as
the anode, an air electrode as the cathode and 4 M KOH solutions with or
without Mannitol as the electrolyte. The concentration range of
mannitol spanned from 0.1 M to 0.35 M, with a concentration of 0.25 M
employed for characterization. The working areas of the two electrodes
were 4 cm2, and the distance between the two electrodes was 2 cm. A
2.0 Ω resistor was connected in series with the aluminum electrode and
the air electrode. An electrochemical workstation (CHI 660D) was
connected into the circuit to record the change of the discharge current.
The re-discharge performance of the aluminum electrodes was
assessed through a discharge process of an Al-air battery in a 4 M KOH
solution containing mannitol as the additive. The polished Al alloy was
immersed in a 4.0 M KOH solution with mannitol to discharge for half an
hour at a temperature of 50 ◦ C. Thereafter the electrode was removed
from the solution and placed into a box with a temperature of 45 ◦ C and
a humidity of 80–100 (simulate the electrode environment after drain­
ing the electrolyte) for 24 h to form a corrosive product film on the
surface of the electrode, and then put into an oven at 50 ◦ C for 24 h to
dry the film formed on the surface. The electrode was named as re-
discharge electrode (Fig. S2). The re-discharge electrode was fixed
into the Al-air battery again as the anode, the discharge current - time
curve was recorded, which was named as re-discharge current - time
curve.
2.3. Electrochemical measurements
The polarization curves of the electrodes were measured using a
three-electrode system by electrochemical work station (CHI660D). A
RuO2–Ti mesh (Jin deli New Materials Co., Ltd) was used as the counter
electrodes (CE). A saturated Hg/HgO electrode (0.1 M KOH) was used as
the reference electrode (RE). All the measurements were conducted in
4.0 M KOH solution with and without Mannitol at 25 ◦ C ± 1 ◦ C. The
anodic polarization curves with Al alloy (exposed area, 1 cm2) as the
working electrode (WE) were measured at a potential scan rate of 0.5
mV s− 1. EIS measurements were carried out at the potential with 20 mV
more positive than the open circuit potential and the measuring fre­
quency range was from 0.1 Hz to 100000 Hz. The amplitude of applied
AC perturbation signal was ±5 mV.
2.4. Characterizations of structure and morphology
The surface morphologies of the re-discharge electrode were
observed using an Apreo S LoVac scanning electron microscope (FEI,
USA). The working voltage, current and distance were 5 kV, 50 pA and
10 mm, respectively. The re-discharge electrode was characterized by X-
ray diffraction (XRD, Bruker, D8-Focus) with Cu Kα radiation source (λ
= 1.54 Å). The scanning speed was 8◦ /min.
FT-IR patterns were measured by iS50 FT-IR. The aluminum elec­
trodes used for the measurement were prepared through immersing the
electrode into 4 M KOH aqueous solutions with 0.25 M mannitol for 30
min, and then removed from the solution and naturally air-dried.
2.5. Computational model and details
The calculation related to the interaction between Al (111) slab and
different molecules were performed by using the Vienna ab initio
simulation package (VASP) [22]. Projector augmented wave (PAW)
pseudopotentials were used for calculations. The exchange− correlation
function was calculated within the generalized gradient approximation
(GGA) developed by Perdew, Burke, and Ernzerhof (PBE). The K-point
was generated by the Monkhorst-Pack grid method with 2 × 3 × 1 for
X. Wang et al.
geometry optimization. The cut-off energy was set 450 eV. The SCF
energy convergence and the force on each ion were 10− 4 eV and 0.02 eV
Å− 1, respectively. A 3 × 2 supercell with five-layer Al (111) slab was
used to represent the absorbed surface for molecules. Fixing three layers
of bottom atoms made the top atom relax. A vacuum slab of 20 Å in the
z-direction was used to avoid the interaction between period layers. The
absorbed energy E adsorb between the Al (111) slab and different mole­
cules was defined as the following equation [10]:
E = E Al –E – E molecules
adsorb (111) slab+molecules Al (111) slab
The software package GROMACS was used to perform Classical MD
simulations [24,27]. The SPC/E water model was employed to simulate
[12]. For the preparation of the solution boxes, Packmol packages were
used to build 30 nm × 30 nm × 30 nm boxes containing 200 water, 20
KOH, and 4 mannitol molecules [13]. All simulations used all
three-dimensional periodic boundary conditions and for the simulated
molecules and ions, the General Amber Force Field (GAFF) [24,25]
parameter set was used. Force field parameters generated by Sobtop
software [42]. The simulations were performed for isothermal-isobaric
(NPT) ensemble using 2 fs integration time step for 2 ns. The Berend­
sen thermostat was used to maintain constant temperature of 298 K, and
the Berendsen barostat was used to maintain constant pressure at
1.01325 bar.
The strength of the hydrogen bond between the mannitol and water
molecules was calculated by analyzing the wave function of the
Gaussian optimised structure with the Multiwfn [23,28] software and
the calculations follow the equation [29]:
Fig. 1. (a) XRD patterns and (b) FT-IR spectra of the corrosive products formed in the solutions with and without mannitol, respectively, as well as mannitol powder;
(c) FT-IR spectra of 4 M KOH solutions with different concentrations of mannitol; (d) local FT-IR spectra of figure c).
Journal of Power Sources 592 (2024) 233923
ΔE ≈ − 233.08 × ρ(rBCP) + 0.7423 (2)
where the density of all electrons ρ(rBCP) and H-binding energy ΔE are
in units of a.u. and kcal mol− 1. Structural optimization calculations were
carried out using the Gaussian 16 Quantum Chemistry package [43].
Geometric optimization was performed using the B3LYP correlation
function with DFT-D3 dispersion correction and the 6-311G** basis set.
(1) 3. Results and discussions
3.1. Analyses on the structure and morphology
In order to elucidate the influence of mannitol, the corrosive prod­
ucts formed on the surface of the re-discharge electrode prepared in 4 M
KOH solutions with and without mannitol, respectively, were subjected
to XRD analyses, as depicted in Fig. 1(a) [7]. The XRD pattern of
mannitol powders is also shown in Fig. 1(a) for comparison. The stan­
dard powder XRD diffraction cards were used to interpret the measured
XRD patterns and the results reveal that the diffraction peaks of the
corrosive product formed in 4 M KOH solution correspond to aluminum
hydroxide (Al(OH)3-PDF 20-0011), as well as the underlying aluminum
substrate (Al-PDF 04–0787), respectively. The diffraction peaks of
mannitol also appear in the XRD pattern of the corrosive product formed
in 4 M KOH solution with mannitol except the diffraction peaks of
aluminum hydroxide and the underlying aluminum substrate. This
finding suggests that the corrosion products formed in the solutions with
3
X. Wang et al.
and without mannitol are all composed of aluminum hydroxide, while
the aluminum hydroxide formed in the solutions with mannitol are
mixed with mannitol molecules. The results indicate that mannitol
molecules in the solution does not alter the kind of the corrosive product
although mannitol molecules are embedded into the corrosive product.
The FT-IR spectra of the corrosive products formed in the solution
with 0.25 M mannitol and without mannitol were measured and illus­
trated in Fig. 1(b). The FT-IR spectrum of mannitol powders was also
shown in Fig. 1(b). In terms of mannitol powder, the characteristic peaks
located at wavenumbers ~2900 cm− 1 correspond to C–H vibrations,
while that at wavenumbers 800 cm− 1 to 1480 cm− 1 correspond to C–C
and C–O vibrations [30,31]. These two characteristic peak groups of
mannitol powders all appear in the FT-IR spectrum of the corrosive
product formed in the solution containing 0.25 M mannitol, while that
are not found in the FT-IR spectrum of the corrosive product formed in
the solution without mannitol. The results indicate that mannitol mol­
ecules are imbedded into the corrosive product, which is consistent with
Fig. 2. Surface SEM images of the re-discharge electrodes discharged for 30 min in a 4 M KOH solution (a1-a3) and in a 4 M KOH solution containing 0.25 M mannitol
(b1-b3), respectively; Cross-sectional SEM images of the re-discharge electrodes discharged for 30 min in a 4 M KOH solution (a4) and in a 4 M KOH solution
containing 0.25 M mannitol (b4), respectively.
4
Journal of Power Sources 592 (2024) 233923
the XRD analyses in Fig. 2(a).
To examine the alterations of the hydrogen bonding structure in the
solution, the solutions containing varying concentrations of mannitol
were subjected to FT-IR analyses and the results are shown in Fig. 1(c).
The localized FT-IR spectra of Fig. 1(c) are presented in Fig. 1(d). The
peak located at wavenumbers ~1630 cm− 1 can be attributed to the
stretching vibration peak of H–O–H bonds. With the concentration in­
crease of mannitol molecules in the solution, the wavenumber of the
peaks shifts from 1635 cm− 1 to 1639 cm− 1, indicating an enhancement
in the strength of the H–O–H bond [26,32]. In the solution without
mannitol molecules, the H–O–H bonds exist in the H2O molecules. With
increase of mannitol concentration, the wavenumber of H–O–H bonds
shifts to higher value, revealing that new H–O–H bonds with stronger
bond strength form. It can be supposed that the H atom in H2O mole­
cules and the O atom in the hydroxyl groups existing in mannitol mol­
ecules bond with each other, resulting in the formation of the stronger
new H–O–H bonds.
X. Wang et al.
In order to facilitate a comprehensive comparison of the corrosion
status of electrodes both before and after standby, SEM characterization
was undertaken for each respective condition. Surface SEM images de­
pict electrodes discharged for 30 min in a 4 M KOH solution (Fig. S6(a1-
a3)) and in a 4 M KOH solution containing 0.25 M mannitol (Fig. S6(b1-
b3)). Notably, the introduction of mannitol resulted in the formation of
sparse corrosion products during the discharge process. Furthermore,
cross-sectional SEM images of the electrodes discharged for 30 min in a
4 M KOH solution (Fig. S6(a4)) and in a 4 M KOH solution containing
0.25 M mannitol (Fig. S6(b4)) were analyzed. The cross-sectional ex­
amination revealed that the thickness of corrosion products during the
discharge process, with the addition of mannitol additive, was approx­
imately 10 μm, whereas the thickness of corrosion products without
mannitol was approximately 35 μm. This observation underscores the
proposition that the inclusion of mannitol diminishes the formation of
corrosion products during the discharge process.
To investigate electrode corrosion during standby, SEM character­
ization was conducted on the electrodes following standby, referred to
as "re-discharge electrode". Fig. 2(a1-a3) illustrate the surface SEM
morphologies of the re-discharge electrode discharged for 30 min in a 4
M KOH solution, while that discharged for 30 min in a 4 M KOH solution
containing 0.25 M mannitol are shown in Fig. 2 (b1-b3). Fig. 2(a4) and
Fig. 2(b4) are the cross-sectional SEM morphology of the re-discharge
electrode prepared through the same procedures with that for Fig. 2
(a1-a3) and for Fig. 2(b1-b3), respectively. The biggest differences be­
tween the two kinds of corrosive product are the thickness and the
cracks although the corrosive product all completely covers the surface
of the electrode. It can be found that the surface of the corrosive product
formed in a 4 M KOH solution is continuous and full of long needle-like
corrosive product (Fig. 2(a1-a3)), while that formed in a 4 M KOH so­
lution containing mannitol is full of cracks and the needle-like corrosive
product is very short (Fig. 2(b1-b3)). Combining the surface and cross-
sectional morphologies, it can be found that the corrosive products
formed in both solutions show a double layer structure, and the un­
derlying corrosive product connected with the aluminum alloy is
compact and the upper layer is loose. There is a great difference between
the thickness of the corrosive products formed in the solutions with and
without mannitol. The thickness of the underlying corrosive product
formed in the solutions without mannitol changes from 109.69 μm to
141.52 μm, while that formed in the solutions with mannitol shows a
uniform thickness of ~53.96 μm. The thickness of the long needle-like
corrosive product formed in the solutions without mannitol is in the
range of approximately 80 μm–110 μm. The overall thickness of the
corrosive product formed in the solutions without mannitol is over 220
μm, which is about 4 times larger than that formed in the solutions with
mannitol.
To delve deeper into the disparity in corrosion product quantities
throughout the process, we measured the contact angle of various
electrolytes on the surface of the aluminum electrode (Fig. S7). The
contact angle of the electrolyte with added mannitol on the aluminum
electrode surface is greater than that of the unmodified 4 M KOH elec­
trolyte. Consequently, the residual electrolyte on the aluminum elec­
trode surface post-battery discharge is diminished, thereby lowering the
generation of corrosion products. The results clearly show that the ex­
istence of mannitol in the solution notably diminishes the thickness of
the corrosive product, which can be considered to be caused through
deceasing the residue of the solution on the electrode surface after the
electrode is removed from the solution following the discharge is
stopped. Moreover, the mannitol molecules imbedded in the corrosive
product great increase the internal stress in the corrosive product,
resulting in the formation of the cracks.
3.2. Analyses on the discharge performance
The discharge current density - time (i-t) curves of the as-prepared
aluminum electrodes in 4 M KOH solution with Mannitol in different
5
Journal of Power Sources 592 (2024) 233923
concentration are shown in Fig. 3(a). The discharge current density in
different solution alter almost in the same way: the discharge current
density gets to 83 mA cm− 2 in several seconds and then keep stable.
Fig. 3(b) is the discharge current density - time (i-t) curves of the re-
discharge electrodes in 4 M KOH solution with Mannitol in different
concentrations. It can be found that the discharge current density in
different solutions changes in very different ways. The discharge current
density at the very beginning of discharge (t = 0) and the current when
the discharge current density gets stable are noted as initial discharge
current density and stable discharge current density, respectively. The
initial discharge current density, stable discharge current density as well
as the time for the current density reaches 83 mA are read from Fig. 3(b)
and plotted in Fig. 3(c) and (d), respectively. Combing Fig. 3(b), (c) and
(d), it can be seen that the re-discharge process of the aluminum elec­
trode in 4 M KOH solution exhibits a notably sluggish behavior, with an
initial discharge current density of only 23.79 mA cm− 2, a very long time
(100 min) for the discharge current density to get stable and a very low
stable discharge current density (81.50 mA cm− 2). SEM analyses indi­
cate that the corrosive product formed on the surface of the re-discharge
electrode in 4 M KOH solution is thick and dense, and it completely
covers the surface. The thick and dense coverage of the corrosion
products, aluminum hydroxide, effectively prevents the solution to
contact with the aluminum alloy located below the corrosive product
during the discharge process, and therefore prohibits the discharge of
electrode, resulting in the low initial discharge current density. As the
re-discharge proceeds, the aluminum alloy located below the corrosive
product gradually exposes and the contacting area of the aluminum
alloy with the solution get larger little by little due to the dissolution and
detachment of the corrosive product, leading to a gradual increase in the
re-discharge current density over the time. The prolonged time for the
re-discharge current density to get stable significantly hampers the
practical use of Al-air batteries.
Through adding mannitol as the additive into 4 M KOH solution, the
initial discharge current density surpasses the threshold of 23.79 mA. As
shown in Fig. 3(b), (c) and (d), the maximum initial discharge current
density reaches 76.33 mA when the mannitol concentration in the so­
lution is 0.25 M. The shortest time for the current density reaches 83 mA
and the highest stable current density are 2.6 min and 93.00 mA,
respectively, when the mannitol concentration in the solution is 0.20 M.
Compared with the re-discharge process in 4 M KOH solution, the initial
discharge current density and stable current density increase by 3.2 time
and 1.1 times, respectively, and time for the current density reaches 83
mA is shorten by 38.5 times through adding mannitol into the solution.
The results clearly demonstrate that adding mannitol into 4 M KOH
significantly promote the re-discharge performance of the aluminum
electrode. SEM analyses reveals that there are lots of cracks existing in
the corrosion product formed in the solution with mannitol, and the
thickness of the corrosion product declines by 4 times compared with
that formed in the solution without mannitol. The great amounts of
cracks in the corrosion product effectively promote the solution to
contact with the aluminum alloy located below the corrosive product
and notably accelerate the dissolution and detachment of the corrosive
product at the same time. The thin corrosive product and the cracks in
the corrosive product act together to improve the re-discharge
performance.
To further explore the influence of mannitol as an additive on the
performance of the Al-air battery, a comprehensive evaluation of the
complete battery system was undertaken. The power performance of the
re-discharge electrode was tested at the initiation of the discharge pro­
cess (Fig. S5). The highest power density recorded for the battery
employing a 4 M KOH solution as the electrolyte was 48.48 mWcm− 2 at
a current density of 60.60 mA cm− 2. In contrast, the battery utilizing a 4
M KOH solution containing 0.25 M mannitol as the electrolyte exhibited
a superior performance, achieving a power density of 59.36 mW cm− 2 at
a current density of 74.2 mA cm− 2. This observation leads to the
conclusion that the incorporation of mannitol enhances the re-discharge
X. Wang et al. Journal of Power Sources 592 (2024) 233923

Fig. 3. (a) Initial discharge curves of the as-prepared aluminum electrodes in 4 M KOH solution with different concentrations of mannitol; (b) Discharge curves of the
re-discharge electrodes in 4 M KOH solution with different concentrations of mannitol (c) Relations between the mannitol concentration and the initial current
density (t = 0) as well as the time for the current density reaches 83 mA cm− 2; (c) Relations between the mannitol concentration and the stable discharge cur­
rent density.

performance of the Al-air battery. To ascertain whether the addition of
mannitol has any discernible impact on the normal operation of the
battery, power performance during regular operation was also assessed
(Fig. 4(a)). The open circuit potential (OCP) of the battery in 4 M KOH
solution was measured to be 1.62 V, as shown in Fig. 4(a). However,
with the addition of mannitol as the additive, the OCP slightly decreased
to 1.58 V. The highest power density of the battery with a 4 M KOH
solution as the electrolyte is 64.42 mWcm− 2 at a current density of 78
mA cm− 2, while that with a 4 M KOH solution containing 0.25 M
mannitol as the electrolyte is 62.53 mW cm− 2 at a current density of 77
mA cm− 2. The change in the power density indicates that the addition of
mannitol has minimal effect on the discharge power of the Al-air battery
during normal operation. Furthermore, Fig. 4(b) presents the specific
capacity of the batteries discharged at different current densities in the
solutions with and without mannitol at 50 ◦ C. The specific capacity of
the batteries discharged separately at current densities of 30 mA cm− 2
and 100 mA cm− 2 in 4 M KOH solutions are 320.51 mAh g− 1 and
1052.36 mAh g− 1, respectively. Upon the inclusion of the mannitol

Fig. 4. (a) Relations between the discharge voltage and current density and corresponding power density plots measured in 4 M KOH solutions with and without
mannitol; (b) Discharge specific capacities at different discharge current densities.

6
X. Wang et al. Journal of Power Sources 592 (2024) 233923

additive, the specific capacities of the battery increase to 353.77 mAh

g− 1 at 30 mA cm− 2 and 1344.09 mAh g− 1 at 100 mA cm− 2. The results
indicate that the introduction of mannitol as the additive enhances the
discharge utilization and reduces the energy loss of the aluminum
electrode.

3.3. Analyses on the anodic polarization curves

To have a deep understanding on the electrochemical process of

aluminum electrodes in the solution containing mannitol, the anodic
polarization curves were measured and shown in Fig. 5(a). The current
densities of the curves at potential − 1.2 V in Fig. 5(a) were plotted
against the mannitol concentration and presented in Fig. 5(b). The
current density of the aluminum electrode in 4 M KOH solution at po­
tential − 1.2 V is 87.46 mA cm− 2. It can be found from Fig. 5(b) that the
anodic current density almost linearly declines as increasing mannitol
concentration, although the anodic current density in the solution with
mannitol concentration less than 0.20 M is higher than that in 4 M KOH
solution, and the anodic current density in the solution with mannitol
concentration more than 0.25 M is lower than that in 4 M KOH solution.
The phenomenon that the anodic current density decreases as the
mannitol concentration gets higher can be considered to be caused by
the increase of mannitol molecules adsorbing on the surface of the
electrode, interfering with the anodic electrochemical reaction of Al – 3e
→ Al3+. The interfering effect of the small amount of mannitol molecules
adsorbing on the surface of the electrode is weak while the adsorbed Fig. 6. (a) Electrochemical impedance spectra of the aluminum electrode
mannitol molecules interact with the H2O molecules around the surface. measured in 4 M KOH solutions with different concentrations of mannitol; (b)
It can be presumed that the interaction between the mannitol molecule Equivalent circuit used to simulate the EIS.
and the H2O molecules around the surface of the electrode results in the
anodic current density in the solutions with mannitol concentration less
Table 1
than 0.20 M is higher than that in 4 M KOH solutions. It can be
Impedance parameters of Al in 4 M KOH solution without and with additives.
concluded that a mannitol concentration of 0.25 M yields the most
(component fitting error in parentheses, %).
favorable performance during the re-discharge, as ascertained from a
C (M) R1 (Ω) CPE1 (μF) R2 (Ω) CPE2 (F) R4 (Ω)
combination of the re-discharge curve and the anodic polarization
curve. 0 0.78 (0.47) 74.11 (3.30) 0.30 (1.91) 0.24 (5.02) 0.08 (5.64)
0.10 0.88 (0.42) 99.61 (2.94) 0.40 (2.75) 0.21 (7.62) 0.10 (8.80)
0.20 0.97 (0.43) 79.66 (2.82) 0.45 (3.18) 0.17 (8.60) 0.12 (5.91)
3.4. Analyses on the electrochemical impedance spectra 0.25 0.84 (0.41) 61.36 (2.33) 0.46 (2.20) 0.20 (7.68) 0.13 (6.64)
0.30 0.89 (0.29) 63.86(1.52) 0.48 (1.09) 0.21 (8.08) 0.14 (4.81)
The Electrochemical Impedance Spectroscopies (EIS) of the 0.35 0.94 (0.53) 75.13 (1.52) 0.57 (3.11) 0.13 (5.67) 0.19 (5.66)

aluminum electrode were measured in 4 M KOH solutions with varying

concentrations of mannitol and depicted in Fig. 6(a). The corresponding
equivalent circuit diagram representing the electrochemical process of
the aluminum alloy in the 4 M KOH solution with additives is presented
in Fig. 6(b). The circuit consists of several components: R1 represents the
solution resistance, CPE1 and CPE2 represent constant phase elements,
R2 and R4 represent charge transfer resistors, R3 represents the un­
compensated resistance, and L1 represents the inductive resistance. The
fitted parameters obtained from the analysis are tabulated in Table 1.
All curves in Fig. 6(a) Nyquist diagram consist of three parts: high
frequency capacitive arc, medium frequency inductive arc and low fre­
quency capacitive arc [17]. According to available reports, it was known
that aluminum electrodes undergo a series of oxidation processes in
alkaline solutions such as [18]
Al+OH− →Al (OH)ads+e- (3)

Fig. 5. Anodic polarization curves(a) and corresponding current densities at polarizing potential − 1.2 V(b) of aluminum electrodes in 4.0 M KOH solutions with
different mannitol concentrations.

7
X. Wang et al. Journal of Power Sources 592 (2024) 233923

Al (OH)ads+OH− →Al (OH)2.ads+e- (4) some H2O molecules near the potassium ion are replaced by mannitol
molecules (Fig. 7(b)). New hydrogen bonds are formed between the
(5) mannitol molecules and H2O molecules surrounding mannitol mole­
Al (OH)2, ads+OH− →Al (OH)3.ads+e-
cules, confining the movement of the H2O molecules in this structure.
Al (OH)3, ads+OH− →Al (OH) − 4, ads (6) The numbers of the hydrogen bonds in the simulated system were
calculated and shown in Fig. 7(c). The numbers of hydrogen bonds in
After the addition of mannitol, the diameter of the high-frequency
mannitol-KOH–H2O solution are significantly more than that in
impedance semicircle gradually increases as the concentration in­
KOH–H2O solution, indicating the formation of hydrogen bonds be­
creases from 0.1 M to 0.35 M. This observation suggests that the redox
tween mannitol molecules and H2O molecules. Considering that the
reaction between Al and Al+ controls the rate of charge transfer and
hydrogen bonds are a crucial structural feature in the solution system,
diffusion processes, as indicated by the first capacitance semicircle [34,
the strength of the hydrogen bonds existing in the two solutions was
35]. In the equivalent circuit, R2 represents the corrosion resistance of
calculated and presented in Fig. 7(d). The results indicate that the
the anode and is described in parallel with CPE1. A higher R2 value in­
strength of the hydrogen bond between two H2O molecules is − 21.61 kJ
dicates a greater resistance to corrosion. CPE1 corresponds to the
mol− 1 while that between a mannitol molecule and a H2O molecule is
double-layer capacitance at the interface between the aluminum anode
− 25.31 kJ mol− 1, meaning that H2O molecules preferentially coordinate
and the solution. The presence of an induction loop is attributed to the
with mannitol molecules and stronger hydrogen bonds form in man­
adsorption of intermediates (Al (OH)ads, 1-3 and Al (OH)ads, 4) on the
nitol-KOH–H2O solution. The stronger hydrogen bonds effectively
electrode surface during aluminum dissolution. This loop corresponds to
confine the movement of the H2O molecules in mannitol-KOH–H2O
the inductance L1 and the resistance R3 in Fig. 6(b). The low-frequency
solution, resulting in a kind of "water-grabbing" effect.
capacitive impedance loop is associated with a rapid complementary
H2O molecules as well as mannitol molecules can adsorb on the
redox reaction from Al + to Al3+ [36]. This process is characterized by
surface of Al (111) crystal plane through the oxygen atoms in their
CPE2 in parallel with R4. CPE2 is attributed to the formation of coordi­
structures. The adsorption models and the calculated adsorption en­
nation compounds between aluminum ions and additives [17]. From the
ergies of a water molecule and a mannitol molecule adsorbed on the
Nyquist diagram, it can be concluded that the addition of mannitol does
surface of Al (111) crystal plane are separately shown in Fig. S4. The
not alter the corrosion mechanism of the aluminum electrode in the
calculated adsorption energy of a mannitol molecule on the surface is
alkaline electrolyte. The continuous increase in resistance R2 with
− 74.87 kJ mol− 1 while that for a H2O molecule is only − 12.39 kJ mol− 1,
increasing concentration indicates the suppression of the hydrogen
which means mannitol molecules will preferentially and more strongly
evolution reaction during the discharge process of the aluminum elec­
adsorb on the surface of aluminum electrodes.
trode [37]. This is consistent with the data from the immersion experi­
ments (Fig. S3).

3.6. A proposed mechanism

3.5. MD simulations and DFT calculations
To analyze the impact of mannitol on the solvent structure of the
solution and the hydrogen bonding network, MD simulations were
performed using the GROMACS software. The calculation model as
visualized using VMD [38] is shown in Fig. 7 (a) and (b). Fig. 7 (a) shows
that the potassium ions atomically coordinate with the O atoms in the
H2O molecules in KOH aqueous solution, forming a hydrated shell layer.
The H2O molecules outside the shell layer interconnect through the
hydrogen bonds, creating a hydrogen bonding network among them
[39]. Upon the addition of mannitol, the solvent structure is altered, and
As the Al-air batteries stop to discharge, the alkaline electrolyte, such
as 4 M KOH aqueous solutions, is removed from the cell and then a layer
of the solution remains on the surface of the aluminum electrode, the
negative electrode, resulting in the formation of a dense hydroxide film
completely covering on the surface of the electrode through a corrosion
process. The dense hydroxide film prevents the electrolyte from con­
tacting the aluminum electrode, delaying the discharge when the bat­
teries restart. The corrosion reaction can be described as below:
2Al + 6H2O = 2Al(OH)3 + 3H2↑ (7)

Fig. 7. Snapshot and representative solvation structure models of KOH–H2O solution (a) and mannitol-NaOH–H2O solution, H-bond numbers (c); Binding energy of
the H-bond (d).

8
X. Wang et al.
Fig. 8 gives the schematic view of the structures near the surface of
an aluminum electrode in a 4 M KOH solution as the electrolyte. As
shown in Fig. 8(a), there are lots of H2O molecules adsorbing on the
surface of the electrode. As corrosive reaction (7) proceeds, the adsorbed
H2O molecules constantly combine with aluminum electrode to form
Al3+. Then Al3+ combine with OH− to form Al(OH)3 precipitation to
remove the Al3+ around the electrode. In this way, the corrosive reaction
(7) continually proceeds until the remained solution on the surface is
depleted.
As shown in Fig. 8(b), adding mannitol molecules as the additive into
4 M KOH solution alters the interface structure and the solvent structure
near the electrode. Compared to H2O molecules, the enhanced adsorp­
tive capacity exhibited by mannitol molecules on the electrode surface
results in the nearly complete occupation of said surface. This phe­
nomenon effectively hinders the proximity of H2O molecules to the
electrode surface, consequently leading to a significant reduction in the
quantity of corrosion products. Furthermore, compared with the inter­
action between H2O molecules in the solution, the stronger hydration
ability of mannitol molecules makes H2O molecules prefer to bond with
mannitol molecules, notably confining the H2O molecules near the
surface of the electrode to diffuse to the surface. In addition, strongly
adsorbed mannitol molecules on the surface are imbedded into the
aluminum hydroxide film with the proceeding of corrosive reaction. The
imbedded mannitol molecules cause serious distortion of the aluminum
hydroxide crystal structure and produces internal stress, resulting in the
formation of cracks in the film (Fig. 2(b1)). The existence of great
amounts of cracks in the film acts as the quick channels for the solution
contacting the aluminum alloy substrate underlying the corrosive
product films as the electrode immersing into the solution again, leading
to the instantaneous increase in the current density during re-discharge
process. Comparing with the thick corrosive product film formed in 4 M
KOH solution, the much thinner film full of cracks formed in the solution
added with mannitol further accelerates the dissolution and stripping of
the film. All of these promote the re-discharge current density get up
Fig. 8. Schematic view of the structures near the surface of the electrode in 4 M KOH solution (a) and in 4 M KOH solution added with Mannitol(b).
9
Journal of Power Sources 592 (2024) 233923
quickly to the initial value as shown in Fig. 3(b). These findings offer
valuable insights for the development of aluminum-air batteries with
high performance.
4. Conclusion
Based on an electrode/electrolyte interface adjustment strategy,
mannitol was used as the additive to be added into 4 M KOH solution to
improve the re-discharge performance of Al-air batteries through
reconstructing the adsorptive structure and the solvent structure near
the surface of the aluminum electrode. The introduction of mannitol into
4 M KOH solution facilitates the formation of a much stronger hydrogen
bond between the H2O molecule and the mannitol molecule, disrupting
the original hydrogen bond network formed between the H2O molecules
and establishing a more stable hydrogen bond network between
mannitol and water. This alters the solvent structure near the surface of
the aluminum electrode and greatly suppress the diffusion of the H2O
molecules toward the surface of the electrode during the corrosive re­
action process. Furthermore, the mannitol molecules near the surface
strongly adsorb on the surface of the electrode and almost occupy the
whole surface, which totally changes the interface structure originally
adsorbed with H2O. All of these lead to the formation of a much thinner
corrosive product film covering on the surface of the electrode and the
film is full of cracks causing by imbedding mannitol molecules into the
film to increase the internal stress. The existence of the great amounts of
cracks in the film acts as the quick channels for the solution contacting
the aluminum alloy substrate underlying the corrosive product films and
expedite the removal of the film as the electrode immersing into the
solution again. Compared with the re-discharge process in 4 M KOH
solution, the initial discharge current and stable discharge current in­
crease by 3.2 time and 1.1times, respectively, and the time for the
current density reaches 330 mA is shorten by 38.5 times through adding
mannitol into the solution. Measurements conducted on the Al-air full
battery indicate that the introduction of mannitol has negligible impact
X. Wang et al.
on the power density. The reason for the improvement in the re-
discharge performance is explained reasonably by a proposed mecha­
nism. These findings offer valuable insights for the development of Al-air
batteries with high performance.
CRediT authorship contribution statement
Xuyang Wang: Conceptualization, Data curation, Investigation,
Methodology, Writing – original draft, Writing – review & editing.
Huihui Luo: Validation. Tao Liu: Resources. Lili Zhang: Supervision,
Writing – original draft, Writing – review & editing. Zigeng Liu: Re­
sources, Software, Visualization. Luxia Bu: Writing – original draft,
Writing – review & editing. Wei Wang: Conceptualization, Data cura­
tion, Formal analysis, Funding acquisition, Investigation, Methodology,
Project administration, Resources, Software, Supervision, Validation,
Visualization, Writing – original draft, Writing – review & editing.
Declaration of competing interest
The authors declare the following financial interests/personal re­
lationships which may be considered as potential competing interests:
Wei Wang reports financial support was provided by School of Chemical
Engineering and Technology, Tianjin University, Tianjin 300072, China.
Wei Wang reports a relationship with School of Chemical Engineering
and Technology, Tianjin University, Tianjin 300072, China that in­
cludes:. Wei Wang has patent pending to Wei Wang. No conflict of
interest.
Data availability
Data will be made available on request.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jpowsour.2023.233923.
References
[1] J. Ryu, M. Park, J. Cho, Advanced technologies for high-energy aluminum-air
batteries, Adv. Mater. 31 (20) (2019), e1804784.
[2] Y. Liu, Q. Sun, W. Li, K.R. Adair, J. Li, X. Sun, A comprehensive review on recent
progress in aluminum–air batteries, Green Energy Environ. 2 (3) (2017) 246–277.
[3] D. Gelman, B. Shvartsev, I. Wallwater, S. Kozokaro, V. Fidelsky, A. Sagy, A. Oz,
S. Baltianski, Y. Tsur, Y. Ein-Eli, An aluminum – ionic liquid interface sustaining a
durable Al-air battery, J. Power Sources 364 (2017) 110–120.
[4] H.A.G. Oliver Gröger, Jens-Peter Suchsland, Review—electromobility: batteries or
fuel cells? J. Electrochem. Soc. 162 (14) (2015) A2605–A2622.
[5] C. Wang, Y. Yu, J. Niu, Y. Liu, D. Bridges, X. Liu, J. Pooran, Y. Zhang, A. Hu, Recent
progress of metal–air batteries—a mini review, Appl. Sci. 9 (14) (2019) 2787.
[6] H. Yang, H. Li, J. Li, Z. Sun, K. He, H.M. Cheng, F. Li, The rechargeable aluminum
battery: opportunities and challenges, Angew Chem. Int. Ed. Engl. 58 (35) (2019)
11978–11996.
[7] J. Ren, C. Fu, Q. Dong, M. Jiang, A. Dong, G. Zhu, J. Zhang, B. Sun, Evaluation of
impurities in aluminum anodes for Al-air batteries, ACS Sustain. Chem. Eng. 9 (5)
(2021) 2300–2308.
[8] X.-F. Zhang, R.-J. Chen, Y.-H. Liu, J.-M. Hu, Electrochemically generated sol–gel
films as inhibitor containers of superhydrophobic surfaces for the active corrosion
protection of metals, J. Mater. Chem. A 4 (2) (2016) 649–656.
[9] S. Zhou, C. Tian, S. Alzoabi, Y. Xu, Z. Jiao, K. Luo, B. Peng, C. Zhang, N. Santos,
Y. Cao, Performance of an Al–0.08Sn–0.08Ga–xMg alloy as an anode for Al–air
batteries in alkaline electrolytes, J. Mater. Sci. 55 (25) (2020) 11477–11488.
[10] T. Hu, H. Shi, T. Wei, F. Liu, S. Fan, E.-H. Han, Cerium tartrate as a corrosion
inhibitor for AA 2024-T3, Corrosion Sci. 95 (2015) 152–161.
[11] Y. Zhu, X. Li, D. Zhang, L. Gao, Improvement of electrochemical performance with
amphoteric surfactants for Al anode of Al-air battery in alkaline system, J. Power
Sources 515 (2021), 230646.
[12] E. Faegh, S. Shrestha, X. Zhao, W.E. Mustain, In-depth structural understanding of
zinc oxide addition to alkaline electrolytes to protect aluminum against corrosion
and gassing, J. Appl. Electrochem. 49 (9) (2019) 895–907.
[13] Q. Zhao, P. Wu, D. Sun, H. Wang, Y. Tang, A dual-electrolyte system for highly
efficient Al-air batteries, Chem. Commun. 58 (20) (2022) 3282–3285.
10
Journal of Power Sources 592 (2024) 233923
[14] B.J. Hopkins, Y.S. H, D.P. Hart, Suppressing corrosion in primary aluminum–air
batteries via oil displacement, Science 362 (6415) (2018) 658–661.
[15] J.-M. Koo, H. Araki, S.-B. Jung, Effect of Zn addition on mechanical properties of
brass hollow spheres, Mater. Sci. Eng., A 483–484 (2008) 254–257.
[16] H. Xiong, X. Yin, Y. Yan, Y. Dai, S. Fan, X. Qiao, K. Yu, Corrosion and discharge
behaviors of Al-Mg-Sn-Ga-in in different solutions, J. Mater. Eng. Perform. 25 (8)
(2016) 3456–3464.
[17] J. Liu, D. Wang, D. Zhang, L. Gao, T. Lin, Synergistic effects of carboxymethyl
cellulose and ZnO as alkaline electrolyte additives for aluminium anodes with a
view towards Al-air batteries, J. Power Sources 335 (2016) 1–11.
[18] Y. Liu, H. Zhang, Y. Liu, J. Li, W. Li, Inhibitive effect of quaternary ammonium-type
surfactants on the self-corrosion of the anode in alkaline aluminium-air battery,
J. Power Sources 434 (2019), 226723.
[19] S.-R. Choi, K.-M. Kim, J.-G. Kim, Organic corrosion inhibitor without discharge
retardation of aluminum-air batteries, J. Mol. Liq. 365 (2022), 120104.
[20] Y. Li, Y. Wang, S. Zhang, L. Miao, M. Wei, K. Wang, Corrosion inhibition of
aromatic acids on Al-7075 anode for Al-air batteries with alkaline electrolyte,
J. Power Sources 523 (2022), 231042.
[21] X. Li, J. Li, D. Zhang, L. Gao, J. Qu, T. Lin, Synergistic effect of 8-aminoquinoline
and ZnO as hybrid additives in alkaline electrolyte for Al-air battery, J. Mol. Liq.
322 (2021), 114946.
[22] G.K.J. Furthmüller, Efficient iterative schemes for ab initio total-energy
calculations using a plane-wave basis set, Phys. Rev. B 54 (16) (1996), 11169.
[23] T. Liu, B. Ji, Y. Wu, Z. Liu, W. Wang, Effects of the pH value on the
electrodeposition of Fe–P alloy as a magnetic film material, J. Phys. Chem. C 126
(36) (2022) 15472–15484.
[24] Berk Hess, Carsten Kutzner, David van der Spoel, Erik Lindahl, Gromacs 4:
algorithms for highly efficient, load-balanced, and scalable molecular simulation,
J. Chem. Theor. Comput. 4 (3) (2008) 435–447.
[25] J. Wang, R.M. Wolf, J.W. Caldwell, P.A. Kollman, D.A. Case, Development and
testing of a general amber force field, J. Comput. Chem. 25 (9) (2004) 1157–1174.
[26] T.H. Pham, W.-H. Lee, J.-H. Byun, J.-G. Kim, Improving the performance of
primary aluminum-air batteries through suppressing water activity by hydrogen
bond-rich glycerol solvent additive, Energy Storage Mater. 55 (2023) 406–416.
[27] P. Borthakur, P.K. Boruah, N. Hussain, B. Sharma, M.R. Das, S. Matić, D. Řeha,
B. Minofar, Experimental and molecular dynamics simulation study of specific ion
effect on the graphene oxide surface and investigation of the influence on reactive
extraction of model dye molecule at water–organic interface, J. Phys. Chem. C 120
(26) (2016) 14088–14100.
[28] T. Lu, F. Chen, Multiwfn: a multifunctional wavefunction analyzer, J. Comput.
Chem. 33 (5) (2012) 580–592.
[29] S. Emamian, T. Lu, H. Kruse, H. Emamian, Exploring nature and predicting
strength of hydrogen bonds: a correlation analysis between atoms-in-molecules
descriptors, binding energies, and energy components of symmetry-adapted
perturbation theory, J. Comput. Chem. 40 (32) (2019) 2868–2881.
[30] H. Cheng, T. Wang, Z. Li, C. Guo, J. Lai, Z. Tian, Anode interfacial layer
construction via hybrid inhibitors for high-performance Al-air batteries, ACS Appl.
Mater. Interfaces 13 (43) (2021) 51726–51735.
[31] T. Wang, H. Cheng, Z. Tian, Z. Li, Z. Lin, Z. You, Y. Lu, Y. Zhu, W. Li, Y. Yang,
Q. Zhong, Y. Lai, Simultaneous regulation on electrolyte structure and electrode
interface with glucose additive for high-energy aluminum metal-air batteries,
Energy Storage Mater. 53 (2022) 371–380.
[32] P. Wu, Q. Zhao, H. Yu, Z. Tang, Y. Li, D. Huang, D. Sun, H. Wang, Y. Tang,
Modification on water electrochemical environment for durable Al-Air Battery:
achieved by a Low-Cost sucrose additive, Chem. Eng. J. 438 (2022), 135538.
[33] H. Luo, T. Liu, J. Rageloa, Z. Liu, W. Wang, Effect of cetyl trimethyl ammonium
bromide as an electrolyte additive on secondary discharge performance of
aluminum-air battery, Ionics 29 (5) (2023) 1887–1899.
[34] D. Wang, H. Li, J. Liu, D. Zhang, L. Gao, L. Tong, Evaluation of AA5052 alloy anode
in alkaline electrolyte with organic rare-earth complex additives for aluminium-air
batteries, J. Power Sources 293 (2015) 484–491.
[35] Z. Moghadam, M. Shabani-Nooshabadi, M. Behpour, Electrochemical performance
of aluminium alloy in strong alkaline media by urea and thiourea as inhibitor for
aluminium-air batteries, J. Mol. Liq. 242 (2017) 971–978.
[36] D.D. MACDONALD, Review of mechanistic analysis by electrochemical impedance
spectroscopy, Efecfrochimica Acta 35 (10) (1990) 1509–1525.
[37] C. Zhu, H. Yang, A. Wu, D. Zhang, L. Gao, T. Lin, Modified alkaline electrolyte with
8-hydroxyquinoline and ZnO complex additives to improve Al-air battery, J. Power
Sources 432 (2019) 55–64.
[38] A.D. William Humphrey, Klaus Schulten, VMD: visual molecular dynamics, J. Mol.
Graph. 14 (1) (1996) 33–38.
[39] H. Yu, P. Wu, D. Sun, H. Wang, Y. Tang, Strengthening the hydrogen-bond network
for practical aqueous aluminum–air battery, Ind. Eng. Chem. Res. 61 (34) (2022)
12632–12640.
[40] B.M.L. Rao, R. Cook, W. Kobasz, G.D. Deuchars, in: In IEEE 35th International
Power Sources Symposium, 1992, pp. 34–37.
[41] D. Tzidon, I. Yakupov, Shutdown System for Metal-Air Batteries and Methods of
Use Thereof, 2015. https://patents.google.com/patent/US9627726B2/en.
[42] Tian Lu, Sobtop, Version 3.1, http://sobereva.com/soft/Sobtop.
[43] P.W. Abegg, Ab initiocalculation of spin-orbit coupling constants for Gaussian lobe
and Gaussian-type wave functions, Mol. Phys. 30 (2006) 579–596.
[44] Q.X. Kang, T.Y. Zhang, X. Wang, Y. Wang, X.Y. Zhang, Effect of cerium acetate and
L-glutamic acid as hybrid electrolyte additives on the performance of Al–air
battery, J. Power Sources 443 (2019), 227251.