ECS Transactions, 75 (18) 111-116 (2017)

10.1149/07518.0111ecst ©The Electrochemical Society

Development of Iron-Based Rechargeable Batteries with Sintered Porous Iron

Electrodes

Kazushi Hayashia, Yasutaka Maedab, Tsubasa Suzukib, Hisatoshi Sakamotoa, Toshihiro

Kugimiyaa, Wai Kian Tanb, Go Kawamurab, Hiroyuki Mutob, and Atsunori Matsudab
a
Electronics Research Laboratory, Kobe Steel, Ltd., Kobe, Hyogo 651-2271, Japan
b
Toyohashi University of Technology, Toyohashi, Aichi 441-8580, Japan

We have developed sintered porous iron negative electrodes used

for iron-based rechargeable batteries such as iron-air and nickel-
iron batteries. The water-atomized iron powders having a diameter

that acted as a pore former, and sintered at 1120 C for 20 min in

of a several tens micrometers were mixed with polyvinyl alcohol

N2 atmosphere. The iron electrodes were examined for iron-air

batteries as well as three electrodes cell. Two distinct plateaus
were observed in the discharge curve and the capacity of the iron
air batteries exceeded 100 mAh/g(Fe). The proposed electrodes are
promising for cost effective, highly safe, and environmental
friendly rechargeable batteries.

Introduction

Iron-based rechargeable batteries such as iron-air and nickel-iron batteries are a

promising battery system which could meet the future demands in energy storage systems
for stationary and automotive applications since iron is a cost effective, highly safe,
abundant, and environmental-friendly material.1-3) The iron-based electrodes have
advantages over other metal electrodes like zinc; iron does not form dendrites in the
charge–discharge cycles. A recent state-of-the-art nanotechnology enabling fabrication of
nanostructured iron electrodes provided a higher specific capacity than that of currently-
used lithium-ion batteries, indicating the high potential of iron-based batteries for various
applications.4-8)
One of challenges to secure their high performances is to prevent formation of iron
hydroxide passivation layers onto the electrode surfaces. The successive electrochemical
reaction at the electrode surfaces is gradually terminated with increasing thickness of the
iron hydroxide. A use of iron particles of nanometer size is effective to increase the
specific capacity; however, loading of the adequate iron material may be problematic.8)
Further, the mass production with nanomaterials is inherently costly. Instead, increasing
the effective surface area could be an alternative way to establish both high specific and
total capacity of the batteries. In this study, we have developed iron negative electrodes
consisting of porously sintered iron powders. Atomized iron powders were used as a raw
material in order to realize cost effective, high performance iron-electrodes.

Experimental

111
Downloaded on 2017-03-30 to IP 132.239.1.231 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
 ECS Transactions, 75 (18) 111-116 (2017)

The iron powders formed by water atomization process were used as a raw material. The
diameter of the powders is on the order of several tens micrometers. The iron powders
were mixed with polyvinyl alcohol (PVA) that acted as a pore former, and then injected
into a die. The iron electrode was fabricated by compression forming with a compression
force of 3000 kg/cm2 and sintered at 1120 °C for 20 min in N2 atmosphere. The nominal

electrodes was around 0.5  1 m2/g. The iron electrodes without mixing the PVA were
porosity of the electrode was around 50 %, while the specific surface area of the

also prepared for comparison. The nominal porosity of the conventional electrode was
18 %. Figures 1(a) and 1(b) show the cross-sectional images of (a) the sintered porous
iron electrodes and (b) the normally sintered electrodes.

(a) (b)

100mm 100mm

Fig. 1. Cross sectional images the iron electrodes. (a) Sintered porous iron electrodes. (b)
Normally sintered electrodes.

As an electrolyte, a solution of 8M KOH was used. In some experiments, 0.05 %

K2S was added to the electrolyte. KOH- ZrO2 composites fabricated by sol-gel methods
were also prepared as an electrolyte for feasibility study of all-solid-state iron-air
rechargeable batteries. Detailed fabrication process and their properties were described
elsewhere.9)
Charge-discharge tests were carried out with a three-electrode cell assembly using
the porous iron as the working electrode, Pt as the counter electrode, and Hg/HgO (1M
NaOH) as the reference electrode. For evaluation of the metal-air battery, commercially
available carbon papers with platinum catalyst were employed as the air-electrodes.

Result and Discussion

Figure 2(a) shows the charge–discharge curves of the sintered porous iron electrodes
measured with a three-electrode cell assembly. The electrode was charged for 48 h with a
charge current of 5mA (total charge for each cycle was 533 mAh/g), while the electrode

were observed at around 0.9 and 0.7 V vs. SHE in the discharge curve. The former
was discharged with a current of 5mA (cut-off voltage was 0 V). Two distinct plateaus

reaction is attributed to

112
Downloaded on 2017-03-30 to IP 132.239.1.231 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
 ECS Transactions, 75 (18) 111-116 (2017)

Fe + 2OH− → Fe(OH)2 +2e− Eo = −0.88 V(vs. SHE),

while the latter to
3 Fe(OH)2 + 2OH－ → Fe3O4 + 4H2O + 2e- Eo =―0.65 V (vs. SHE).
The specific capacity of the sintered porous iron electrodes was 140 mAh/g(Fe) at
the first discharge cycle and slightly decreased to 111 mAh/g (Fe) at the third cycle. On

around 20  25 mAh/g(Fe). The specific capacity for the sintered porous iron electrodes
the other hand, the specific capacity of the normally sintered iron electrodes remained

was four times higher than that of the normally sintered one, where the plateaus were
hardly observed, as shown in Fig. 2(b).

Fig. 2. The charge–discharge curves vs. SHE of (a) the sintered porous iron electrodes
and (b) the normally sintered iron electrodes with a three-electrode cell assembly. Charge
current was 5mA (48h) and discharge current was 5mA.

Figure 3 shows the specific capacity of the sintered porous iron electrodes as a
function of cycling. The charge current was 50mA (4.8h) and the discharge current was
5mA. The evaluation was carried out by a three electrodes cell. The specific capacities of
the initial 8 cycles were gradually decreased with cycling and the reduction by 25 % of
the specific capacity was observed. After one week intermission, the sintered porous iron
electrode showed a specific capacity of around 75 mAh/g(Fe) and was stable up to the 18
cycles of measurements. The specific capacity of the first cycle of the second term (9 th
cycle) was reduced, probably due to self-discharge of the iron electrodes.

113
Downloaded on 2017-03-30 to IP 132.239.1.231 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
 ECS Transactions, 75 (18) 111-116 (2017)

200

Capacity / mAh/g (Fe)

1 week intermission
150

100

50

0
2 4 6 8 10 12 14 16 18
Cycle number

Fig. 3. Specific capacity of the sintered porous iron electrodes as a function of cycling.

To improve the cycle performances of the sintered porous iron electrodes, K2S was
added to electrolyte, as sulfur is known as an additive to suppress the degradaiton.6)
Figures 4 show results of cyclic voltammograms (C-V) obtained from (a) KOH and (b)
KOH + 0.05 % K2S electrolytes. The scan speed was 30 mV/s and the cycle number was

0.5 and 0.8 V vs. Hg/HgO. This result indicates that the electrochemical reaction
1- 30 cycles. By adding small amount of K2S, two peaks were clearly observed around

between iron and oxygen was enhanced by preventing from formation of iron hydroxide
passivation layers.

350 350
(a) KOH (b) KOH +K2S
Current density [mA/cm2]
Current density [mA/cm2]

0 0

-350 -350
-1500 -1000 -500 0 -1500 -1000 -500 0
Potential [mV vs.Hg/HgO]
Potential [mV vs.Hg/HgO]

Fig. 4. Cyclic voltammograms (C-V) obtained from (a) KOH and (b) KOH + K2S
electrolytes. Scan speed was 30 mV/s. Cycle number was 1- 30.

The operation as the iron-air battery was examined using Pt-loaded carbon paper as
an air electrode. Figure 5 shows the charge–discharge curves of the iron-air batteries
equipped with the sintered porous iron electrodes. The electrolyte was KOH with and
without additional K2S. The charge current was 5mA (48h) and discharge current was
5mA. Two distinct plateaus were observed at around 0.8 and 0.6 V in the discharge curve,
confirming the operation as a secondary metal-air battery. The operating voltage was

114
Downloaded on 2017-03-30 to IP 132.239.1.231 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
 ECS Transactions, 75 (18) 111-116 (2017)

lower than theoretically predicted value due to presence of over potential originating
from the air electrodes. The specific capacity of the battery without addition of K2S was
90 mAh/g(Fe) for the first cycle and reduced at 60 mAh/g(Fe). By adding K2S in the
electrolyte, the performances were improved, as expected by C-V, to 120 mAh/g(Fe) for
the first cycle and around 90 mAh/g(Fe) for the second and the three cycles. These results
demonstrate the proposed porous iron electrodes consisting of atomized iron powders
exhibit a high performance secondary batteries.

2.5

2
1cycle
Potential (V)

charge 2cycle
1.5
3cycle
Fe(0) 1cycle
discharge
1 →Fe(II) Fe(II)
2cycle
→Fe(III) 3cycle

0.5 With
Without K2S
K2S
0
0 50 100 150
Capacity [mAh/g(Fe）]

Fig. 5 Charge–discharge curves of iron-air batteries equipped with the sintered porous
iron electrodes as a negative electrode. Electrolyte was 8M KOH with and without K2S.

Finally, all-solid-state iron-air rechargeable batteries with KOH- ZrO2 composite

electrolyte were evaluated. The structure of the battery was shown in Fig. 6(a). As shown
in Fig. 6(b), operation as a secondary battery was confirmed. However, the discharge
curves were degraded with cycling. It is speculated that the contact area between the iron
electrodes and the composite electrolyte was not sufficient due to the sandwich structure
of the battery. Further improvement of the properties is required since the solid state
rechargeable batteries are durable and operatable in wide temperature range.

Conclusion

Sintered porous iron negative electrodes have been developed for application to iron-
based rechargeable batteries such as iron-air and nickel-iron batteries. It was found that
two distinct plateaus were observed in the discharge curve and the capacity of the
batteries exceeded 100 mAh/g(Fe). The operation as the iron-air battery using Pt-loaded
carbon paper as an air electrode was also confirmed. Preliminary results for all-solid-state
iron-air rechargeable batteries with KOH- ZrO2 composite electrolyte were presented.
These results demonstrate porous iron electrodes consisting of atomized iron powders are
promising for rechargeable iron-air batteries.

115
Downloaded on 2017-03-30 to IP 132.239.1.231 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
 ECS Transactions, 75 (18) 111-116 (2017)

(a) (b)

Fig. 6(a) Structure of the all-solid-state iron-air rechargeable batteries with KOH- ZrO2
composite electrolyte. (b) Charge–discharge curves of all-solid-state iron-air batteries
equipped with the sintered porous iron electrodes as a negative electrode.

References

1. J. Christensen, P. Albertus, R. S. Sanchez-Carrera, Timm Lohmann, B. Kozinsky,

R. Liedtke, J. Ahmed, and A. Kojic, J. Electrochem. Soc. 159, R1 (2012).
2. Md. A. Rahman, X. Wang, and Cuie Wen, J. Electrochem. Soc. 160, A1759
(2013).
3. R. D. McKerracher, C. P. de Leon, R. G.A. Wills, A. A. Shah, and F. C. Walsh,
ChemPlusChem, 80, 323 (2015).
4. A. K. Manohar, S. Malkhandi, B. Yang, G. K. S. Prakash, and S. R. Narayana, J.
Electrochem. Soc. 159, A1209 (2012).
5. A. K. Manohar, C. Yang, S. Malkhandi, G. K. S. Prakash, and S. R. Narayana, J.
Electrochem. Soc. 160, A2078 (2013).
6. A. K. Manohar, C. Yang, and S. R. Narayana, J. Electrochem. Soc. 162, A1864
(2015).
7. E. Shangguan, F. Li, J. Li, Z. Chang, Q. Li, X.-Z. Yuan, and H. Wang, J. Power
Sources. 291, 291 (2015).
8. Y. Maeda, et al. Extended Abstract of The 55th Battery Symposium in Japan,
p.470 (2014) (in Japanese).
9. A. Matsuda, H. Sakamoto, T. Kishimoto, K. Hayashi, T. Kugimiya, and H. Muto,
Solid State Ionics, 262, 188 (2014).
10. T. Tsuneishi, T. Esaki, H. Sakamoto, K. Hayashi, G. Kawamura, H. Muto, A.
Matsuda, Key Engineering Materials, 616, 114 (2014).
11. T. Tsuneishi, H. Sakamoto, K. Hayashi, G. Kawamura, H. Muto, A. Matsuda, J.
Asian Ceramic Soc. 2, 165 (2014).

116
Downloaded on 2017-03-30 to IP 132.239.1.231 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).