Journal of Power Sources 326 (2016) 296e302

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Journal of Power Sources

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

Carbon treated commercial aluminium alloys as anodes for

aluminium-air batteries in sodium chloride electrolyte
 n b, E. Fata
M. Pino a, b, D. Herranz a, J. Chaco  n a, *
s a, P. Oco
a
Universidad Auto s y Valiente 7, 28049, Madrid, Spain
noma de Madrid, Facultad de ciencias, Departamento Fsico Qumica Aplicada, calle Francisco Toma
b
Albufera Energy Storage S.L., Parque Cientco de Madrid, Campus de Cantoblanco, calle Faraday 7, 28049, Madrid, Spain

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

Carbon treated commercial Al alloy

anodes achieve discharges up to 3
times longer.

Al1085 alloy performs better at low
current rates, while Al7475 at high
rates.

Carbon Black achieves best behav-
iour/price ratio vs Pyrolytic Graphite
and Graphene.

Specic capacities of 1200 mAh g1
are achieved, and 2 V plateaus in
4s1p battery.

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

Article history: An easy treatment based in carbon layer deposition into aluminium alloys is presented to enhance the
Received 17 March 2016 performance of Al-air primary batteries with neutral pH electrolyte. The jellication of aluminate in the
Received in revised form anode surface is described and avoided by the carbon covering. Treated commercial Al alloys namely
17 May 2016
Al1085 and Al7475 are tested as anodes achieving specic capacities above 1.2 Ah g1 vs 0.5 Ah g1
Accepted 28 June 2016
Available online 9 July 2016
without carbon covering. The inuence of the binder proportion in the treatment as well as different
carbonaceous materials, Carbon Black, Graphene and Pyrolytic Graphite are evaluated as candidates for
the covering. Current densities of 1e10 mA cm2 are measured and the inuence of the alloy explored. A
Keywords:
Metal-air
nal battery design of 4 cells in series is presented for discharges with a voltage plateau of 2 V and 1
Aluminium-air Wh g1 energy density.
Commercial alloys 2016 Elsevier B.V. All rights reserved.
Carbon treatment
Neutral pH electrolyte

1. Introduction
One of the most promising applications for aluminium is found
in metal-air batteries, which have special interest for future use in
electric vehicles (EV) [1,2] and large-scale energy storage systems
(ESS) [3]. The major advantage of this technology compared to
* Corresponding author.
E-mail addresses: mikel.pino@albufera-energystorage.com (M. Pino), pilar.
n).
ocon@uam.es (P. Oco
other batteries is the fact that atmospheric oxygen is used in the
cathodic side instead of a stored reagent, allowing a space and
weight reduction. Additionally, the oxygen source is inexhaustible
so the specic energies of these batteries is just limited by the
anode. Among the different metals, aluminium exhibits a high
negative standard potential of 1.676 vs. SHE [4] and a high theo-
retical energy density of 8076 Wh kg1 [5]. Besides, Al is the fourth
most abundant element in the crust and it is distributed through
different areas, contrary to lithium or other typical energy storage
materials [6] that are located in a few countries. Thus, price and

http://dx.doi.org/10.1016/j.jpowsour.2016.06.118
0378-7753/ 2016 Elsevier B.V. All rights reserved.
 M. Pino et al. / Journal of Power Sources 326 (2016) 296e302
availability of the resource stays constant in time. The latter,
coupled with a low production cost and easy recycling processes
leads to an easily available and cheap material.
Aluminium is a well-known construction and manufacturing
material due to its lightness and toughness, and is extensively used
in automotive, aerospace or infrastructure industries. There is a
great variety of commercial alloys classied as function of the
mayor alloying. Most of these alloys are focused in enhancing the
mechanical properties of the resulting metal, and so, alloying ele-
ments like Fe, Mg, Zn or Si are commonly present. The use of
commercial alloys as anodes in Al-air batteries could make a rev-
olution in low-cost energy storage. The main problem is the
spontaneous formation of an oxide lm in the Al surface when in
contact with air or aqueous media. The latter results in a protective
layer covering the electrode that shifts the corrosion potential in
the positive direction and the reactivity of the aluminium is slowed
down notoriously [5,7e10]. This change causes a signicant
reduction in the available energy and makes Al, in principle, un-
attractive as an energy storage material. Nevertheless, many
research groups have focused on developing an Al-air cell because
of his high theoretical cell voltage of 2.4 V, and specic capacity of
2978 mAh g1, comparable to that of lithium 3840 mAh g1, and
much higher than the ones for Na or Zn, 1165 and 830 mAh g1
respectively.
Many studies are focused in alkaline electrolyte [11e15] because
of the high cell potential (in practice up to 2 V) and high current
discharges. The major issue is that in highly alkaline concentrations
the self-corrosion reactions of Al become notorious, to result in
constant hydrogen evolution and uncontrolled aluminium mass
lose [16,17]. These secondary reactions sentence the cell to a short
useful life once the electrolyte is in contact with the Al electrode,
and hinder the nal design of the battery owing to the need to
evacuate massively generated H2 and heat. Other studies are
focused in neutral salt-water electrolyte [18e20] because of the low
self-corrosion rate. But the lower cell potential due to the worst
performance of the oxygen reduction reaction (ORR) in the positive
air electrode, and partial solubility of the formed Al(OH)3 during
the discharge results unattractive for exploiting all the capacity of
aluminium. This aluminate results in the formation of a gel around
the anode as described Despi c et al. [21], that impedes the diffusion
of hydroxyl ions to the Al, and so the battery dies early. Besides, the
low hydroxyl ion conductivity of this electrolyte leads the cell to
low discharging current rates compared to those in alkaline media
[17].
Several strategies have been explored for enhancing the per-
formance of the Al-air cells. Tailored Al alloys have attracted the
attention from many research groups and companies. It is reported
that trace amounts of metals like Ga, In or Sn in a high purity Al
matrix shift the reduction potential of the alloy to more negative
values permitting higher cell voltages [22]. Additionally, the
columbic efciency is increased and the corrosion minimized [7].
Several companies as Alupower or Alcan registered a good deal of
patents related to the composition and formation process of
tailored Al alloys for energy harvesting in the 1970s. The principal
disadvantage is the high cost of the resulting alloy (high purity
metals needed) and the difculty of the alloying process due to big
differences between melting points (Ga 29.77  C vs Al 660.3  C).
Due to the latter, once the alloy is conformed, thermal treatments
are needed to achieve homogeneous composition all over the
metal. Other strategies focus on the addition of metallic salts into
the electrolyte, mainly to increase the reactivity of Al surface or to
prevent the formation of Al(OH)3 gel. It is reported that abrasives
like NaF or Na6AlF3 can punch the native aluminium oxide layer
[23], increasing the activity points of the anode. Other additives like
metal-amines or aromatic compounds can x the aluminate to
297
make it precipitate, not limiting the diffusion of OH ions to the
anode surface.
In this work we present an easy and cheap method to enhance
the discharging behaviour of commercial Al alloy anodes in neutral
electrolyte Al-air battery. The formation of the aluminate gel
around the anode was found to be due to the interaction between
AleAl2O3eAl(OH)3 in the electrode surface. By incorporating
carbonaceous materials on the alloy surface the adherence of the
aluminate was slowed down considerably, as R. Mori described
[24,25], allowing the precipitation of the formed gel. This method
tolerates a higher use of the aluminium mass, achieving discharges
up to 1200 Ah$kg1 with quite at potential evolution. To face the
low cell potential a 3D printed 4s1p battery (4 cells in series by 1 in
parallel) was designed and measured, achieving discharges up to
5 mA$cm2 with voltage plateaus of 2 V. This simple design results
in a low-cost, easily made primary battery for energy supply in
remote locations.
2. Experimental
2.1. Electrodes and materials
Commercial aluminium alloys, Al1085 and Al7475, with a car-
bon treatment were evaluated as anodes in neutral electrolyte Al-
air batteries; Table 1 reports their compositions. Both alloys are
well-known materials and are extensively used in industries such
as automotive and building. These alloys were chosen since they
represent an inexpensive and accessible input for the actual
industries.
Three types of carbonaceous materials for the anode treatment
were evaluated: Carbon Black (CB, Cabot Corp., USA), Graphene
(RGO, NanoInnova, Spain) and Pyrolytic Graphite (PG, Lurederra
T.C., Spain). Polyvinylidene diuoride (PVdF) and N-Methyl-2-
pyrrolidone (NMP) from Sigma-Aldrich were chosen as binder
and solvent respectively.
The electrolyte of the battery consisted in saltwater (2 M NaCl).
A commercial air cathode named E4A, from Electric fuel, was
used as the positive electrode in these Al-air cells. It consists in a Ni
mesh on which carbon with a MnO2 catalyst is pasted. On the air-
exposed face, a lm of O2-permeable Teon is pressed to pre-
vent liquid electrolyte leakage, while allowing oxygen to diffuse
readily from the ambient atmosphere toward cathode-electrolyte
interface.
2.2. Electrode preparation: carbon treatment
Aluminium alloy anode: pieces of 3 cm2 exposure area (each
face) were used as anodes (20 mm H x 15 W x 1e2 T). The samples
were polished with emery paper (grade 200e800) and then
cleaned with distilled water and acetone. The weight of each plate
ranged between 0.9 and 1.3 g depending on the sample thickness.
Carbon treatment: the paste was prepared by mixing 2 parts of
carbonaceous material, 1 part of binder and 7 parts of solvent (by
weight). The inuence of the binder percentage was studied by
varying the ratio between carbon and binder (2:1, 4:1 and 9:1). The
mix resulted in a medium-viscous paste, which was homoge-
neously dispensed over the alloy sample surface. For higher area
Table 1
Chemical compositions of the different grades commercial aluminium alloys (wt%).
Alloy sample Si Fe Cu Mn Mg Cr Zn Ti Others
Al7475 0.02 0.09 1.2 0.06 2.2 0.2 5.7 0.06 e
Al1085 0.1 0.16 0.03 0.02 0.02 e 0.03 0.01 Ga V: 0.01
298 M. Pino et al. / Journal of Power Sources 326 (2016) 296e302
treatments a spray ink can be obtained by increasing the amount of
solvent. Once the paste/ink was extended, the NMP was evaporated
in an oven at 120  C for 12 h. Finally, the treatment resulted in a
homogeneous thin black coverage all over the aluminium plate.
2.3. Cell assembly
For the cell assembly a 3D printed ABS (Acrylonitrile Butadiene
Styrene) structure was patterned by a structure design software.
Both sides of the case and lateral covers were trimmed to enable
the contact of the air cathodes with the electrolyte and atmosphere
air respectively. The electrodes were attached between two 0.5 mm
thick silicone lms to ensure sealing. So, Al anode total area was
6 cm2 (both faces), and the cathode area was 8 cm2 (4 cm2 by Al
side), slightly oversized to avoid limiting the anode behaviour.
For the 4s1p battery a 3D printed ABS structure was also
designed. 12 cm2 aluminium anodes were assembled against same
area air electrodes in four isolated cubicles within the cell structure.
The electric contacts were made of cupper to ensure a good electric
conductivity.
2.4. Electrochemical measurements
The electrochemical tests were carried out using a 12-channel
Arbin Instruments BT2143 workstation at room temperature
(25  C). Once the cell was assembled a 5 min period was left to
allow good impregnation of electrodes to stabilize the open circuit
potential (OCP). The cut-off potential for all cases was 0.0 V. Con-
stant current density discharges of 1e10 mA$cm2 were applied to
explore the evolution of the potential. Discharging times and spe-
cic capacities referred to Al mass were recorded. Polarization
curves were also measured in half-cell at room conditions and scan
rate of 1 mV$s1. All measurements were repeated at least three
times to ensure reproducibility.
3. Results and discussion
Fig. 1 shows the improvement in the discharge prole of the Al1-
air neutral cell by using the carbon treatment in the surface of the
aluminium anode. First tests were carried out with the Al1 covered
with Carbon Black layer as anode. Owing to our previous experi-
ence [26] the composition of this alloy, high aluminium content,
performs better at low current ranges than Al7 alloy with Zn as
majority alloying metal content. Carbon Black was the rst choice
thought low price and easy availability. As shown in Fig. 1a, Al1
alloy treated with CB at a current density of 6 mA cm2 performed a
0,9
Al-air / 2M NaCl / 6 mAcm
0,8
0,7
-1
Al1-CB / 740 mAhg
0,6
0,5
E/V
0,4
0,3
-1
0,2 Al1 / 230 mAhg
0,1
a)
0,0
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28
Time / hours
Fig. 1. Discharge plot of Al1-air cell with vs without carbon cover at constant current density of: a) 6 mA cm2; b) 1 mA cm2.
three time longer discharge than the one without coating, resulting
in a specic capacity of 740 against 230 mAh g1. The cell potential
was also slightly higher reaching a at plateau at 600 mV till the
end of the discharge. In Fig. 1b applied current density was
1 mA cm2 and resulted in a similar improvement of the dis-
charging time (around three times longer). The potential of the cell
evolved quite at between 700 and 650 mV and suddenly decayed
because of the complete consumption of the electrolyte water ac-
cording to the anodic oxidation reaction (1):
Al OH 2H2 O/AlOH3 H2 [ (1)
The nal appearance of the cell was a completely crystallized
Al(OH)3 NaCl mix covering both electrodes.
On the contrary, the performance of Al1 without carbon treat-
ment at 1 and 6 mA cm2 respectively, was prevented because of
the total covering of the aluminium anode by the aluminate gel,
without total water consumption.
The formation of a gel during the discharge of the battery im-
pedes the diffusion of the hydroxyl ions formed during the oxygen
reduction reaction (ORR) process in the cathode, and so the battery
gets exhausted prematurely. Aluminium hydroxide is the product
of the oxidation of the Al-air battery. This compound results highly
soluble in acidic media while precipitates in alkaline media. In
neutral pH region the solubility of the aluminate results partial and
gives rise to the formation of a jelly texture whitish product. The
adherence of this gel into the aluminium anode is quite high, and
so, it grows up around all the anode area till the Al sample is
completely rounded. This phenomenon was appreciated also in the
polarization curves of the alloys tested in this work, see Fig. 2. In
both cases, Fig. 2a and b, the current density of carbon treated alloys
increased rapidly. Nevertheless, in the case of the bare alloys, the
potential of the Al was moved to more positive values for same
current density values. This behaviour is closely related to the
accumulation of aluminate in the electrode surface and nally this
becomes in a higher loss of Al-air cell potential during the discharge
process due to the anode over-potential.
Fig. 3 shows a scheme of the comparison between the Al-air cell
discharge with and without carbon treatment and how does it in-
uence in the formation of the gel. The adherence of the aluminate
into the CB layer results signicantly lower than the one on metallic
aluminium surface (AleAl(OH)3eAl2O3 mix). Due to this property
and the higher density of the aluminate compared to the electro-
lyte, the gel tends to precipitate not rounding the anode, and not
limiting the discharge of the battery. Through this method the
partial solubility of the Al(OH)3 remains unchanged, but it permits
the sedimentation of the cited compound and so, in advanced cell
-2 0,9
Al-air / 2M NaCl / 1 mAcm-2
0,8
0,7 Al1-CB / 630 mAhg-1
0,6
0,5
Al1 / 285 mAhg-1
E/V
0,4
0,3
0,2
0,1
b)
0,0
0 10 20 30 40 50 60 70 80 90 100
Time / hours
 M. Pino et al. / Journal of Power Sources 326 (2016) 296e302 299

150 150
Al1 / 2M NaCl Al7 / 2M NaCl
135 135
120 120
105 105
90 90
-2

-2
j / mAcm

j / mAcm
75 75
Al1-CB Al1 Al7-CB Al7
60 60
45 45
30 30
15 15
a) b)
0 0
-0,9 -0,8 -0,7 -0,6 -0,5 -0,4 -0,3 -0,2 -0,1 0,0 -1,0 -0,9 -0,8 -0,7 -0,6 -0,5 -0,4 -0,3 -0,2 -0,1
E / V (vs Ag/AgCl) E / V (vs Ag/AgCl)

Fig. 2. Polarization curves, at scan rate of 1 mV1 and 298 K in half-cell with and without carbon layer of: a) Al1; b) Al7.

Fig. 3. Schematic representation of aluminate accumulation in Al-air neutral pH cell with and without carbon treatment.

designs the formed product could be extracted from the button of 0,9
the cell continuously, limiting not at all the discharge behaviour. Al-air / 2M NaCl / 10 mAcm-2
0,8
The extracted gel could be treated then to recover water and
0,7
metallic aluminium as described S. Zaromb for a primary Al-air
alkaline battery in the early 60s [27]. 0,6
Al7 alloy was also tested at 1 and 6 mA cm2 but as pointed out 0,5
E/V

above, the obtained results were lower in terms of cell potential Al7-CB / 1210 mAhg-1
0,4
and specic capacity, despite the carbon treatment. Nevertheless,
at higher current densities (10 mA cm2) Al7 performed a long time 0,3
discharge while Al1 alloy was not able to achieve more than 4 h. Al7 / 540 mAhg-1
0,2
Fig. 4 shows the discharge behaviour of the Al7 alloy with and
without carbon treatment vs treated Al1 at 10 mA cm2. As 0,1
Al1 / 195 mAhg-1
mentioned the potential of the Al1 anode cell decayed quickly, 0,0
0 3 6 9 12 15 18 21 24 27 30 33 36
performing a plateau of just 1 h near 350 mV. The initial over-
Time / hours
potential compared to those at 1 and 6 mA cm2 was higher due
to the fast demand of hydroxyl ions in the surface of the negative Fig. 4. Discharge plot of Al1 and Al7-air cells with vs without carbon cover at constant
electrode. It is reported that the OH conductivity of the electrolyte current density of 10 mA cm2.
limits signicantly the maximum current available for fuel cells
[28] and consequently for metal-air cells. Nonetheless CB treated
Al7 anode cell performed the higher specic capacity discharge of The better behaviour of the Al7 at higher current ranges vs Al1 at
the present work, achieving 1210 mAh g1. Cell potential stabilised lower current rates can be explained as the fact that alloying ele-
at 400 mV for a plateau of 32 h and a nal drop to 200 mV due to the ments like Zn, Mg and Cu (present in the Al7 alloy) lead to galvanic
release of an aluminium portion, and nally the discharge ended. corrosion in the surface of the anode, that compete with the
Compared to that without carbon treatment the performance was 2 oxidation of the aluminium at low current rates. To the extent that
times longer and the potential evolution more stable. The latter Al is oxidised, the cited metals get release in the electrolyte origi-
proved the effectiveness of the proposed carbon treatment nating galvanic pairs that induce the aluminium to corrode,
regardless of the employed aluminium alloy. competing with the anodic oxidation. This phenomenon was
300 M. Pino et al. / Journal of Power Sources 326 (2016) 296e302

extensively treated in one of our previous works [16]. When the 0,9
Al-air / 2M NaCl / -Al1-CB / 1 mAcm-2
current density is greater, the galvanic pairs are not so dominant 0,8 -Al7-CB / 10 mAcm-2
compared to Al oxidation, and the discharge performance is Al1-2:1 / 630 mAhg-1
0,7
enhanced. Additionally, alloying Zn is able to drag Al to is oxidised
as was demonstrated by Wang et al. [29], originating new active 0,6 Al1-4:1 / 624 mAhg-1
points in the electrode surface. Contrary, Al1 alloy (high aluminium 0,5

E/V
content >99.7%) performed better at low current rates due to a
cleaner oxidation process, not impeded by secondary processes of 0,4

the impurities. 0,3 Al7-4:1 / 1190 Al7-2:1 / 1210

Table 2 reports a brief summary of different aluminium anodes mAhg-1 mAhg-1
0,2
studied by some investigation groups for Al-air batteries with
neutral pH electrolyte. Tailored aluminium alloys seems to enhance 0,1

in a notable way the performance of the cell, achieving discharges 0,0

of 20 mA cm2 with high cell potentials above 1.2 V. Nevertheless
the price of the resulting alloy results quite high and actually non-
commercial. In the case of pure aluminium (5 N), the behaviour of
the cell is similar to the one of the Al7 commercial alloy, however
the price of this last results two orders of magnitude cheaper. A
similar result for commercial Al 1050 alloy is also reported, but
discharging times and available currents are lower. All this behav-
iour results of the double cathode cell design and the enhanced
performance due to the carbonaceous treatment.
Two ways were explored to enhance the performance of the
carbon treatment: rst, optimising the binder proportion in the
carbon ink, and second, trying different carbonaceous materials.
New proportions of carbon:binder, 4:1 and 9:1, were tested to
ensure that the high initial binder content (2:1) was not limiting
the movement of hydroxyl ions and the evacuation of aluminate.
First attempt with 9:1 proportion resulted unsuccessful. The carbon
layer presented very low mechanical resistance and get detached
just by manipulation of the negative electrode to assemble the cell.
On the contrary the 4:1 proportion, allowed manipulation and
presented similar resistance to scratching and adhesion to those of
initial percentage. Fig. 5 shows the discharge behaviour of Al1 and
Al7 treated with CB, 2:1 vs 4:1 proportion, at 1 and 10 mA cm2
respectively. There were no signicant differences in the voltage
plateaus and discharging times so it was concluded that the binder
quantity was only affecting the adhesion and resistance of the
cover. So, once reached a minimum proportion of PVdF in order to
ensure the mechanical properties, the electrochemical behaviour of
the cell was not affected by the binder percentage.
The inuence of the carbonaceous material was studied by
substituting CB by RGO and PG. The preparation of the carbon ink/
paste was the same, and the obtained coating presented similar
mechanical resistance. Fig. 6 shows the discharge behaviours of Al1
and Al7 treated with CB, RGO and PG at 1 and 10 mA cm2. Gra-
phene treated alloys performed a quite similar prole to the ones
with Carbon Black. In both cases, 1 and 10 mA cm2, the discharging
time was slightly lower due to a small variation in the thickness of
0 10 20 30 40 50 60 70 80 90 100
Time / hours
Fig. 5. Discharge plot of Al1 and Al7-air cells with CB cover at constant current density
of 1 and 10 mA cm2, respectively: 4:1 vs 2:1 binder proportion.
Al plate and consequently the weight. The RGO covered anodes
performed quite at potential plateaus that could be related to: (a)
the lower particle size compared to CB, that permit a good
dispersion in NMP and the obtained paste resulted easier to
dispense homogeneously in the aluminium anode; and (b) the
more laminar structure of the material, that generates preferential
paths for the chemical species inlet and evacuation. On the con-
trary, PG treated anodes demonstrated lower cell potential and
specic capacity. This was found to be because of the high porosity
of the material that gave rise to the accumulation of aluminate in
the pores. In this way, even if the precipitation of the aluminate was
possible, a little amount of Al(OH)3 get xed in the surface of the
negative electrode hindering the arrival of hydroxyl ions and
evacuation of new formed aluminate. Besides, PG resulted difcult
to dispense or spray because it is a bad dispersion in the paste, and
so, the obtained layer was thicker than the ones with CB or RGO.
Once explored the pathways for optimising the carbon treat-
ment, the binder proportion was xed in 2:1 to ensure a maximum
adhesion of the carbon layer and the carbonaceous material selected
was CB. In spite of the little advantage of the RGO vs CB, the price of
the last resulted more than 100 times cheaper and the scalability
more feasible. Considering the achieved results, it was decided to
develop a new cell that could reach higher voltages for more real-
istic applications. A 3D printed 4s1p battery was designed, see Fig. 7,
to rise the cell potential up to 3.4 V in open circuit. The battery was
based in the previous unity cells pattern but the positive-negative
electrode proportion was reduced to 1:1 to ease the design. The
four compartments were completely divided to avoid electrolyte
transfer, and the upper side of the cell was silkscreened to ensure
the isolation between the copper electrical contacts.

Table 2
Current densities, ECell, discharging time and price comparison of different Al-air neutral pH batteries in bibliography.

Al anode Electrolyte Current (mA cm2) ECell (V) Time (hours) Price (V/kg) Assignee Ref

5 N Al e UFG 2 M NaCl 10 0.388 3a >100 L. Fan et al. [11]

5 N Al e CG 0.399
Al-Mg-Ga-Sn-Mn 2 M NaCl 20 1.236 5a >200 J. Ma et al. [8,18]
Al-Mg-Ga-Sn 1.185
Al-Mg-Zn-Ga-Sn 1.09
Al 1050 NaCl 1 0.67 62 1.4 R. Mori [24]
2 0.64 28
3 0.58 7
Al 1085 2 M NaCl 1 0.65 94 1.2 Present work
6 0.6 26
Al 7475 10 0.4 34 1.6
a
Partial discharge.
 M. Pino et al. / Journal of Power Sources 326 (2016) 296e302 301

0.9 0,9
Al-air / 2M NaCl / -Al1 / 1 mAcm-2 Al-air / 2M NaCl / -Al1 / 1 mAcm-2
0.8 -Al7 / 10 mAcm-2 0,8 -Al7 / 10 mAcm-2
Al1-CB / 630 mAhg-1 Al1-CB / 630 mAhg-1
0.7 0,7

0.6 0,6
Al1-RGO / 610 mAhg-1
0.5 0,5 Al1-PG / 505 mAhg-1

E/V
E/V

0.4 0,4

0.3 Al7-RGO / 1200 Al7-CB / 1210 0,3

mAhg-1 mAhg-1 Al7-PG / 1080 Al7-CB / 1210
0.2 0,2
mAhg-1 mAhg-1
0.1 0,1
a) b)
0.0 0,0
0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100
Time / hours Time / hours

Fig. 6. Discharge plot of Al1 and Al7-air cells with carbon treatment at constant current density of 1 and 10 mA cm2, respectively: a) CB vs RGO; b) CB vs PG.

Resulting battery potential did not correspond to the theoretical

data achieved with the unity cells at 6 mA cm2. It was expected
that the total cell potential once polarized at 5 mA cm2 to be at
least 2.4 V. The latter is related to losses because of the electric
contacts and the worst operation of the air electrodes in a pro-
portion 1:1 to anodes, without oversizing.
The presented carbon treatment has demonstrated the capacity
to increase the discharge behaviour of commercial aluminium al-
loys in neutral pH electrolyte. Al1 and Al7 are easily available
metals and CB is a quite cheap and common carbonaceous material.
The latter along with the simple 4s1p 3D printed battery structure,
and easily reproducible and scalable methods could give raise to
Fig. 7. Schematic representation of 3D printed 4s1p Al-air battery.
the development of simple and robust sea water activated com-
mercial batteries.

CB treated Al1 was the chosen anode for this battery because the 4. Conclusions
selected current density for the test was 5 mA cm2 to achieve a
high battery potential above 2 V. Besides, the manipulation of the Al Carbon coating was found to be an easy and effective treatment
plate resulted easier because the high aluminium content, more for aluminium-air cell anodes in neutral pH electrolytes. Carbona-
malleable than Al7. Fig. 8 shows the discharge of the 4s1p battery at ceous material layer exhibited a minimised adherence to generated
5 mA cm2, using Al1 alloy as anode treated with CB carbon cover. aluminate during discharge, permitting the sedimentation of the
The evolution of the battery potential resulted quite at with a formed gel. This allowed the aluminium anode to be active for more
constant value of 2 V during 18 h till a sudden nal decay. This than three times longer, compared to non-coated electrodes.
battery achieved a specic capacity of 480 mAh g1 per gram of Al1 was found to perform better at current densities below
aluminium in a discharge of 5 mA cm2, which corresponds to an 6 mA cm2 showing specic capacities higher than 700 mAh g1,
energy of 1 Wh g1. while Al7 behaviour as anode resulted better at current rates of
10 mA cm2 for capacities of 1200 mAh g1. This ndings are
consisted with the formation of galvanic pairs in the electrode
surface (mostly in Al7) that induce Al to corrode. This corrosion
3,6
process competed with the oxidation of Al, getting minimised at
3,3 Al-air / 2M NaCl / 5 mAcm-2
higher currents densities.
3,0
The binder percentage in the carbon treatment paste/ink was
2,7 identied to inuence the mechanical resistance of the coating but
2,4 not the electrochemical behaviour of the cell. Among all tested
4s1p cell: Al1-CB / 1 Whg-1
2,1 carbonaceous materials CB was found to exhibit the better perfor-
E/V

1,8 mance/price rate, even of the little advantage of RGO ink in the
1,5 dispensing or spraying. The use of a 3D printed structure as battery
1,2 can was showed for developing an easy and cheap 1 Wh g1 saline
0,9 Al-air battery. A 4s1p conguration was designed to achieve
0,6 discharge plateaus of 2 V at a current of 5 mA cm2 for 18 h.
0,3
0,0
0 2 4 6 8 10 12 14 16 18 20
Acknowledgments
Time / hours

Fig. 8. Discharge plot of 3D printed 4s1p Al1-air battery at a constant current density The authors would like to acknowledge the FUAM-ALBUFERA
of 5 mA cm2. ENERGY STORAGE Project for funding.
302 M. Pino et al. / Journal of Power Sources 326 (2016) 296e302

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