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DOI 10.1007/s11581-016-1785-z
ORIGINAL PAPER
Preparation of Schiff base surfactant and its application
in alkaline zinc-nickel batteries
Zheng Liu 1 & Yong Zhao 1 & Guo-Cheng Han 2 & Jin Liu 1 & Qiuyi He 1 & Chenzheng Chen 2
Received: 19 April 2016 / Revised: 10 July 2016 / Accepted: 19 July 2016
# Springer-Verlag Berlin Heidelberg 2016
Abstract A Schiff base surfactant 2-octanone ethylene
diamine (OED) was in this study designed to improve the
performance of alkaline zinc-nickel batteries that were synthe-
sized and characterized by IR and XRD. Electrochemical ex-
perimental results showed that addition of OED surfactant in
both zinc electrode and electrolyte effectively inhibited self-
corrosion of zinc electrode and improved performance of zinc-
nickel battery charge and discharge. The battery capacity can
keep almost 70 % of the theoretical capacity after 30 times
cycles. The batteries also showed better performance, lower
resistance, and longer cycle life with addition of surfactant,
which can be attributed to fact that the zinc electrode surface
had good adsorption capacity and coordination with zinc ions
in the presence of surfactant.
Keywords Zinc electrode . Self-corrosion . Dendrites .
Deformation . Surfactant
Introduction
Zinc is one of the widely used negative electrode materials for
batteries such as nickel-zinc batteries, silver zinc batteries,
* Zheng Liu
lisa4.6@163.com
* Guo-Cheng Han
hangc1981@163.com
1
Department of Chemical and Biological Engineering, Guilin
University of Technology, Guilin 541004, People’s Republic of
China
2
School of Life and Environmental Sciences, Guilin University of
Electronic Technology, Guilin 541004, People’s Republic of China
zinc-air batteries, and common manganese batteries. Zinc
owns many electrochemical properties with higher hydrogen
over-potential, smaller corrosion loss, higher uniform anode
erosion, and working potential when compared with magne-
sium, lithium, or aluminum materials [1–3].
There are currently several challenges that still hamper the
development of alkaline zinc batteries or zinc electrode as an
anode material. Such challenges include the following: solu-
bility in alkaline solution, deformation, dendrite growth, self-
corrosion, and inactivation [4–6]. In order to solve the above
challenges for zinc electrode, preparation processes for zinc
electrode, collector materials, electrode charge and discharge
system, membrane materials, and additives have been studied
extensively [7–10]. Some specific additives were especially
added in the zinc electrode and electrolyte to improve the
corrosion performance for secondary zinc electrode [11–15].
It is well known that mercury is one of the best kinds of zinc
electrode additives. It was found that addition of 1~4 wt%
HgO to the electrode can effectively improve the performance
of zinc electrode [16, 17]. However, mercury and mercury
salts pollute environments for a long time, and they should
thus be abandoned as zinc electrode additives.
Surfactant inhibitors play more and more important role as
zinc electrode additives [18], because they form corrosion
adsorbed films on the surface layer of zinc electrode, which
not only have a leveling effect by inhibiting self-corrosion of
zinc electrode but also increase polarization of zinc electrode
and uniform zinc deposition layer. The ideal surfactants
should be therefore be easily adsorbed on the surface of neg-
atively charged zinc metal containing O, N, S, P heteroatoms
and own π-electron system. They should also easily bond with
zinc atoms or ions and generate appropriate hydrophilic or
hydrophobic molecular chains. Such kinds of surfactants
should be soluble in alkaline electrolytes and should have
good adsorption rate on zinc electrode, making sure of the

Scheme 1 Synthesis route for
OED
formation of full corrosion hydrophobic adsorption films on
the surface of zinc electrode, which can be used to improve the
performance of alkaline zinc-nickel batteries.
This study designed a Schiff base surfactant 2-octanone
ethylenediamine (OED) to improve the performance of alka-
line zinc-nickel batteries. Electrochemical methods were car-
ried out to investigate the improved performance of alkaline
zinc-nickel batteries after addition of surfactant. The methods
included cyclic voltammetry, polarization curves, and electro-
chemical impedance. Comparative experiments were execut-
ed under different situations, such as no addition of surfactant
in the electrolyte or on the electrode, addition of surfactant on
the electrode, addition of surfactant in the electrolyte, and both
addition of surfactant on the electrode and in the electrolyte.
Experimental
The Schiff base surfactant 2-octanone ethylenediamine (OED)
was synthesized according to Scheme 1.
2-Octanone (3.2 mL, 20 mmol) was dissolved in 15 mL of
dried ethanol at 50 °C, followed then by immediate addition of
0.6 eq. ethylenediamine (0.8 mL, 12 mmol). Glacial acetic
acid (1.0 mL) was added into the above solution as catalyst.
After stirring for 3 h, the solution was cooled down to 2 °C
and glacial acetic acid was removed. Ethanol was then evap-
orated and orange slurry was obtained. The slurry was recrys-
tallized and dried at 50 °C and orange powder was obtained
(1.845 g, 72.1 %). IR (KBr, cm −1 ): υ C=N = 1563, υ s,
CH3 = 2933, υs, CH2 = 2855, δCH = 1404, and υC-N = 1328.
SEM images of zinc electrodes were carried out by scan-
ning electron microscopy (JEOL.TSM-6380LV), at accelera-
tion voltage of 12 kV and magnification of 1500 times.
After polishing of the bare zinc sheet (1 × 3 cm) with
abrasive paper, it was sonicated in Milli-Q water, followed
by acetone and water. The zinc sheet sheets were finally dried
by nitrogen gas. Next, the top of zinc sheets (1 × 2 cm) was
sealed with Teflon tape and the left bottom (1 × 1 cm) was
taken as zinc electrode for use. The zinc electrode was pasted
with a mixture of 0.6 g zinc oxide, 0.3 g zinc powder, and
0.05 g colloidal graphite, using 60 % PTFE as a binder.
Different concentrations (2, 4, and 5 % mass fraction) of 2-
octanone ethylenediamine Schiff base surfactant (OED) were
added on the copper substrate [19–22].
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1.5 g of zinc oxide was added in 50 mL of 6 mol/LKOH
solution with constant stirring; 6 mol/L KOH of saturated
electrolyte was then obtained after dissolving zinc oxide.
Different concentrations (2, 4, and 5 % mass fraction) of 2-
octanone ethylenediamine Schiff base surfactant (OED) were
added into the electrolyte for further use as corrosion
additives.
A CHI860B electrochemical workstation (Chenhua
Instruments, Beijing, China) was used to perform all electro-
chemical experiments. The electrochemical cell was a classi-
cal three-electrode system with zinc electrode as the working
electrode, saturated calomel electrode as reference electrode,
and nickel sheet (2 × 5 × 1 cm) as counter electrode which was
polished and washed before every experiment to make sure
every measurement was available [23]. All potentials were
referenced to the potential of the saturated calomel reference
electrode.
For testing of E-logi curves, the scanning range was
−1.5 ~ −0.8 V with scan rate of 0.001 V/s. The sensitivity of
the system was set automatically.
For testing of electrochemical impedance spectroscopy,
measurements were carried out at the open circuit potential
of −1.423 V vs. Hg/HgO electrode at amplitude modulation
of 5 mV and frequency range of 0.01 Hz to 10 kHz.
For testing of cyclic voltammetry, the scanning range was
0.25~0.55 V, with scanning rate of 0.01 V/s, the number of
scan segments being 200.
For testing of charge-discharge, the charging current was
set as 10 mA for charging 4 h, and the discharge current was
Fig. 1 IR spectra from OED
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Fig. 2 SEM images of zinc
electrode with different additions
OED in electrolyte (a blank; b
4 % addition OED)
set as 20 mA, with 1.0 V discharge termination voltage for
30 cycles of charge-discharge.
Results and discussion
Figure 1 shows IR spectra from OED. It can be seen that the
peak at 1563 cm−1 was regarded as stretching vibration of
C=N and peaks at 2933 and 2855 cm−1 belonged to stretching
vibration of CH3 and CH2, respectively. The peak for CH
flexural vibration is shown at 1404 cm−1, while the peak at
1328 cm−1 was attributed to stretching vibration of C–N, re-
spectively. These IR spectra results confirmed the synthesis of
OED according.
Moreover, the zinc electrodes were scanned by SEM after
immersion of electrodes in electrolyte at different additions of
OED (a: blank; b: 4 % addition OED) as shown in Fig. 2.
It can be seen that the zinc electrode that was immersed in
electrolyte without addition of OED (Fig. 2a) had obvious
signs of corrosion while with 4 % addition of OED
(Fig. 2b), the zinc electrode looked smooth, with smaller de-
gree of corrosion happening when compared to no addition of
OED. This was due to OED being adsorbed on the surface of
Fig. 3 E-logi curves for zinc electrodes with different additions of OED
the zinc electrode, forming a protective film that effectively
inhibited corrosion of the zinc electrode [24].
For electrochemical experiments, the polarization experi-
ments were first executed. Figure 3 shows the E-logi curves of
zinc electrode with different additions OED (A: blank; B: 2 %
OED; C: 4 % OED; D: 5 % OED).
After addition of OED into the electrolyte, the potential
moved from −0.97 to −1.01 Vand the corrosion current values
decreased at the same time, indicating that the OED had inhi-
bition effect. The best inhibition effect was shown when the
addition of OED was up to 4 % (mass fraction), with change
of corrosion current value from 0.166 to 0.024 mA. These
results also suggested that the OED was a cathode type of
corrosion inhibiting additive, mainly inhibiting hydrogen evo-
lution reaction of cathode and slowing down the rate of anodic
zinc decomposition reaction at the same time. The corrosion
of zinc electrode was therefore weakened.
The electrochemical impedance spectra from the two sys-
tems involving control solution (blank) with addition of OED
were fit to the equivalent circuit as shown in Fig. 4. The circuit
shows a number of circuits in series as may be expected for a
film that was constructed using a stepwise build-up of the
surface architecture [25], where Rs, Rct, and CPE represented
solution resistance, electrochemical reaction resistance, and
double-layer capacitance, respectively.
Figure 5 shows AC impedance curves for zinc electrode
with different additions of OED (A: blank; B: 2 % OED;
C:4 % OED; D: 5 % OED), and Table 1 shows the electro-
chemical impedance parameters for zinc electrode with differ-
ent additions of OED.
The impedance curves appeared with better semicircles
after addition of OED (Fig. 5 B, C, D). The semicircle
Fig. 4 Equivalent circuit diagram for AC

Table 1 Electrochemical
impedance parameters of zinc Surfactants Content (%)
electrode with different additions
of OED Blank 0 0.25856
OED 2 0.38814
4 0.39754
5 0.40543
diameter increased significantly with increasing OED content,
indicating that the electrode reaction process was controlled
by electrochemical reaction. The increase of electrochemical
impedance can slow the corrosion reaction [26], so addition of
OED can effectively prevent or inhibit corrosion. From
Table 1, the inhibition efficiency (η) values of B, C, and D
for the surfactants were 91.3, 94.7, and 95.1 %, respectively.
It is well known that zinc electrode often forms dendrite
and deformation in alkaline conditions, leading to damage of
zinc electrode and greatly reducing its service life. Cyclic
voltammetry curve can reflect the stability of zinc electrode
charge-discharge process in an alkaline electrolyte [27].
Typically, the instability of peak current and potential will
indicate that the zinc electrode may form dendrite and defor-
mation, affecting the charge-discharge process. The cyclic
voltammetry curves can therefore be used to assess whether
the additive can effectively inhibit the zinc electrode from
forming the dendrite and deformation [2].
Figure 6 shows CV curves of zinc electrode with different
additions of OED (a: blank; b: 4 % OED addition on zinc
electrode; c: 4 % OED addition in electrolyte) with 2 laps,
20 laps, 50 laps, and 100 laps scan, respectively.
From Fig. 6a, it can be seen the current value increased
with increasing scan times, especially after 50 times scan.
The current change from 0.018 to 0.027 A indicated unstable
electrode in the charge-discharge process, where zinc dendrite
and deformation may be caused. This is because the zinc den-
drites growth in zinc electrodes in the charging process has
Fig. 5 AC impedance curve of zinc electrode with different additions of
OED
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Rs/Ω cm2 Rct/Ω cm2 CPE1-T CPE1-P η (%)
18.380 0.0010527 – –
211.90 0.0189120 0.82025 91.3
346.80 0.0136700 0.78780 94.7
378.05 0.0016795 0.82251 95.1
greater solubility for generating zincate in alkaline solution
where the process of matter transfer becomes difficult. Zinc
ions are easily deposited at the electrode surface, leading to
dendrite formation and deformation [28]. With addition of 4 %
OED on zinc electrode (Fig. 6b) or in electrolyte (Fig. 6c), the
current value of oxidation peak and potential value of oxida-
tion peak have no significant change with increasing scan
times, even after 100 times scan, indicating that the charging
and discharging process were much more stable. The capacity
of battery was almost kept the same, the electrochemical pro-
cess being quasi-reversible. The addition of OED on the elec-
trode and in the electrolyte can inhibit zinc electrodes forming
dendrite and deformation. It was thus concluded that the syn-
thesized OED formed complexes with zinc ions that were
easily adsorbed on the surface of zinc electrode. The zinc ions
could therefore be supplied enough for zinc deposition in the
battery charges [29].
The final purpose of this study was to improve the perfor-
mance of alkaline zinc-nickel batteries by addition of OED on
electrode and in electrolyte, which should base on results from
the batteries charge-discharge experiments [30]. Figure 7
shows the curves from battery first discharge at different time
points (A: blank; B: 4 % OED addition on zinc electrode; C:
4 % OED addition in electrolyte; D: both 4 % OED addition
on zinc electrode and in electrolyte).
It is known that nickel-zinc batteries that are composed of
pasted zinc electrode and nickel electrode have a good charge
and discharge platform. The charging platform was raised up
to 1.9~2.0 V, with discharge plateau about 1.5 V. There was no
big difference between the potential of charge and discharge,
indicating a reversible charge and discharge process. The
nickel-zinc battery had a longer discharge time and higher
discharge voltage when compared with the blank group.
This is because the OED could inhibit zinc electrode from
forming corrosion dendrites and deformation under alkaline
conditions. The nickel-zinc battery had a higher discharge
capacity. The order for four-group discharge capacity was ob-
tained as D > B > C > A. The charge and discharge perfor-
mance for the nickel-zinc batteries was therefore improved by
addition of OED both on the electrode and in the electrolyte,
but addition of OED on the electrode was better in the elec-
trolyte (B > C), because the OED has adsorption property
when attached on the electrode, preventing the electrode ma-
terial from falling off from the copper substrate. The charge-
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Fig. 6 CV curve for Zinc electrode with different additions of OED (a blank; b 4 % OED addition on zinc electrode; c 4 % OED addition in electrolyte)
discharge process effectively inhibited corrosion of the elec-
trode and dendrite formation and deformation [31, 32].
The capacity for the alkaline zinc batteries gradually de-
cays during continuous charge and discharge process, even
leading to scrapping of battery, mainly because the zinc elec-
trode becomes corrosive, forming dendrite and deformation,
and damaging the zinc electrode. The charge and discharge
experiment of assembled batteries is an effective manner to
Fig. 7 Curves of battery first discharge at different time
investigate the cycle performance of pasted zinc electrode
[33]. Figure 8 shows the capacity curves for 30 times batteries
charge and discharge (A: blank; B: 4 % OED addition on zinc
electrode; C: 4 % OED addition in electrolyte; D: both 4 %
OED addition on zinc electrode and in electrolyte).
It can be learnt that the capacity of assembled nickel-zinc
batteries was enhanced at the beginning 3 times cycles and
then gradually decreased during the charge and discharge
Fig. 8 Capacity curve for 30 times battery charge-discharge

process. This is because the nickel-zinc batteries have an ac-
tivation process during the first 3 cycles and then gradually
decreases due to pasted zinc electrode becoming corrosive,
forming dendrite and deformation, and even damaging the
batteries during the 30 times cycles. Taking control group
(A) as an example, the capacity almost decayed to zero after
30 times cycles; for C, the battery capacity kept 15 % of total
theoretical capacity, while the battery capacity kept 50 % of
total theoretical capacity for B. For D, the battery capacity
almost kept 70 % of the total theoretical capacity. The order
for the four-group theoretical capacity after 30 times cycles
was obtained as D > B > C > A, which was consistent with the
results from the nickel-zinc batteries first discharge [34–37].
Conclusions
A Schiff base surfactant 2-octanone ethylenediamine (OED)
was successfully synthesized in this study, to improve the
performance of alkaline zinc-nickel batteries. Electro
chemical experiment results showed that addition of surfactant
OED both on zinc electrode and in electrolyte effectively
inhibited the self-corrosion of zinc electrodes and improved
the performance of zinc-nickel battery charge and discharge.
The battery capacity could almost keep 70 % of the theoretical
capacity after 30 times cycles, which were attributed to the
zinc electrode surface having good adsorption capacity and
coordination with zinc ions in the presence of OED surfactant.
Acknowledgments The work was supported by the National Natural
Science Foundation of China (2126606 and 61301038), Guangxi Natural
Science Foundation of China (2012GXNSFAA053034 and
2015GXNSFBA139041), and Collaborative Innovation Center for
Exploration of Hidden Nonferrous Metal Deposits and Development of
New Materials in Guangxi.
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