Electrochimica Acta 59 (2012) 64–68

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Lead ion and tetrabutylammonium bromide as inhibitors of the growth of spongy

zinc in single flow zinc/nickel batteries
Yuehua Wen a,∗ , Tian Wang b , Jie Cheng a , Junqing Pan b , Gaoping Cao a , Yusheng Yang a,b
a
Research Institute of Chemical Defence, Beijing 100191, China
b
College of Science, Beijing University of Chemical Technology, Beijing 100029, China

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

Article history: Lead ion and tetrabutylammonium bromide (TBAB) have been testified as inhibitors of spongy zinc
Received 19 September 2011 electro-growth from flowing alkaline zincate solutions. To assess the efficacy of the two additives,
Received in revised form 10 October 2011 current–time technique using potentiostatic electro-deposition, scanning electron microscopy and
Accepted 12 October 2011
cycling test were undertaken. The results show that the growth of spongy zinc in flowing alkaline zincate
Available online 9 November 2011
solutions can be effectively inhibited by the addition of 10−4 M Pb(II) or TBAB at the cathodic potential
( = −100 mV), respectively. But, the dual addition of 10−4 M Pb(II) and 5 × 10−5 M TBAB produces more
Keywords:
effective suppression on spongy zinc growth. Obvious synergistic effect of Pb(II) and TBAB on the inhi-
Electrolyte additive
Spongy inhibition
bition of spongy zinc deposits is found. From the charge/discharge cycling tests of the single flow Zn–Ni
Lead ion test cells, it is shown that the rechargeability of Zn anode is highly improved by the mixed introduction
Tetrabutylammonium bromide of 10−4 M Pb(II) and 5 × 10−5 M TBAB.
Single flow Zn–Ni battery © 2011 Elsevier Ltd. All rights reserved.

1. Introduction use of additives are combined with the charge–discharge perfor-

mance of zinc-based secondary batteries. Additives such as Bi2 O3
Secondary zinc-based batteries are usually limited in their [9,10], Pb3 O4 [11] and quaternary ammonium compounds [12]
performance and widespread commercialization by poor cycling have the beneficial effect on the performance of zinc electrodes.
characteristics of zinc anode [1]. The short cycle life of zinc anode Recently, it was found by us that some inorganic additives such as
mainly arises from dendritic growth and shape change with the lead, Na2 WO4 , etc. were also effective to suppress the formation
zinc electrode during charging. So far, many attempts including the of spongy zinc deposits from flowing electrolyte [13]. This kind of
use of additives in either the electrode or the electrolyte have been additives with favorable chemical stability could be alternatives of
undertaken [2–4]. Although the cycle life and properties of zinc electrolyte additives in alkaline single flow zinc–nickel batteries.
electrodes are improved to some extent, the problem still remains In this present work, the effects of lead ions and tetra-
elusive [5–7]. In 2007, Cheng et al. proposed a novel redox flow bat- butylammonium bromide (TBAB) as electrolyte additives on the
tery system, namely, single flow zinc–nickel battery [8]. Compared morphology, spongy growth and electrochemical behavior of
with the conventional solid zinc electrodes, the reaction of zinc deposited zinc electrodes in flowing electrolytes were studied, and
electrodes turns into the deposition and dissolution process of zinc. their synergistic effect was also discussed. The logical aim of the
Thereby, this kind of zinc electrode can be called ‘deposited-zinc study is to optimize the concentration of the two additives so that
electrode’. During the charge/discharge cycle of this system, the the deposited zinc electrode has good electrochemical behavior,
concentration polarization is substantially reduced due to the use of minimum spongy growth with a view to fabricate an alkaline single
flowing electrolytes. The zinc dendrite growth might be prevented flow zinc–nickel system. Subsequently, the battery performance of
effectively. The cycling performance of zinc electrodes is improved this system with the two electrolyte additives is evaluated.
considerably. Nevertheless, spongy zinc deposits are easy to form
from flowing alkaline zincate solutions during the charge. Thus, the 2. Experimental
performance of batteries is influenced to a significant degree.
The use of additives in stationary electrolytes to inhibit the den- All solutions used were freshly prepared using analytical grade
drite growth has been widely studied. However, few studies on the chemicals and deionized water. A 8 M KOH solution containing
0.7 M ZnO and 20 g L−1 LiOH was used as the blank solution. The
additives such as lead ions or tetrabutylammonium bromide (TBAB)
∗ Corresponding author. with different concentrations were added into this solution. The
E-mail address: wen [email protected] (Y. Wen). current–time measurements were undertaken by a three-electrode

0013-4686/$ – see front matter © 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2011.10.042
 Y. Wen et al. / Electrochimica Acta 59 (2012) 64–68 65

configuration using a polished Ni sheet (with an area 1 cm2 ) as the the rise in the cathodic deposition current of zinc in the flowing
working electrode, while Hg/HgO (6 M KOH) as the reference elec- blank solution is large (from about 75 to 226 mA). It indicates that
trode, and a large Ni gauze as the counter electrode, respectively. even in flowing solutions, the deposition of zinc is still controlled
The working electrode was insulated using epoxy resin except the by mass transport polarization to a large degree which may result
surface to be tested. Before each experiment, the electrode was pol- in the formation of loose and more “open-structured” deposits.
ished with emery paper (1000 grade), degreased with acetone and Visual observation did find heavy spongy zinc deposits formed
rinsed with deionized water. on the electrode surface. The addition of TBAB in the electrolyte
Current–time curves were acquired using an electrochemical produces flatter current–time responses. With the concentration
working station (Solartron 1280z) at a constant cathodic over- of TBAB increasing, the rise of the deposition current during test
potential ( = −0.1 V). The surface morphology of deposits was decreases. At the onset of zinc deposition, a sharp reduction in cur-
assessed by a scanning electron microscope (Cambridge, S-360). rent is observed, which may be caused by the formation of crystal
The measurements were performed under the magnetic stirring of cores. The higher the concentration of TBAB, the more obvious is
electrolytes and at room temperature of 25 ◦ C. this phenomenon. Nearly flat current–time profiles are observed
The charge/discharge cycling tests were conducted using a bat- with the TBAB additive of 10−4 M and higher. When the content of
tery test system CT2000A (Jinnuo Wuhan Corp., China) on test TBAB in the electrolyte is 10−4 M, the current–time profile is not
cells of NiOOH|8MKOH + 0.7 M ZnO + 20 g L−1 LiOH with/without only almost flat but also the cathodic deposition current is closed
additives|Zn to explore the performance of the proposed elec- to the initial current in the blank solution. This indicates that the
trolytes. This cell consisted of three main parts, the positive formation of spongy zinc can be effectively inhibited and the charge
and negative electrodes and the concentrated alkaline electrolyte efficiency of the deposited zinc electrode will not be decreased
which was pumped by a magnetic drive pump. Two sheets of significantly by the addition of 10−4 M TBAB.
folded sintered nickel electrodes and one sintered nickel electrode Fig. 2 depicts the current–time profiles with different concentra-
(7 cm × 7 cm, 0.31 mm thick) were placed on both sides of a nickel- tions of the lead additive. Similar to the case of TBAB addition, the
plated perforated steel strip (0.1 mm thick) which was the negative efficacy of adding lead ions on the spongy zinc inhibition is raised
electrode substrate. It guaranteed that the capacity of the positive with increasing lead concentration. As low a concentration as of
electrode exceeded that of the negative electrode, so as not to limit 5 × 10−5 M, the flattening of cathodic current is obvious. The cur-
the cycling of the battery. The cell compartment was filled with the rent changes from 66 to 134 mA (compared with that of the blank
studied electrolytes. Before test, the sintered nickel hydroxide elec- solution 75–226 mA) during the 60 min test. When the lead concen-
trodes with an area capacity of 25 mAh cm−2 were pre-activated. tration is increased to 5 × 10−4 M, the cathodic current is inhibited
The size of the positive and negative electrodes is 7.0 cm × 7.0 cm. to a low value, i.e., ∼40 mA. It exhibits a much lower current value
In the charge–discharge cycles, the cell was charged at a current than the initial current in the blank solution before the onset of
density of 20 mA cm−2 until the capacity reached 20 mAh cm−2 and spongy zinc growth. Thus, the optimal concentration of lead ions
discharged at the same current density down to 1.2 V cut-off. The should be 10−4 M even though the current–time curve is not com-
flow rate of electrolyte is 19.5 cm s−1 . Temperature throughout this pletely flat. In addition, compared with the organic additive TBAB,
study was about 25 ◦ C. a significant reduction in current at the onset of zinc deposition is
not observed in the electrolyte with the lead additive. It may be
3. Results and discussion attributed to the different effect mechanisms of additives.

3.1. Effects of Pb(II) and TBAB on the spongy growth of zinc 3.2. Synergistic effect of Pb(II) and TBAB

The current–time curves of zinc in the flowing alkaline zin- Mixed addition of lead ions and TBAB was undertaken for fur-
cate solutions with and without TBAB at a cathodic overpotential ther investigations under the higher speed of magnetic stirring.
 = −100 mV are shown in Fig. 1. Since any rise in cathodic current As shown in Fig. 3, the individual addition of 10−4 M lead ions
during a potentiostatic electrodeposition is assumed to be due to or TBAB produces flatter current–time responses, but the rise of
an increase in true electrode surface area, the variation in current the cathodic current is still obvious, especially for the addition of
versus time at constant potential reflect sensitively the change in TBAB. The almost flattened current–time curve depicts that syn-
surface morphology (roughness). It can be seen from Fig. 1 that ergistic effect occurs by the dual addition of lead and TBAB with

0.00 3 0.00

-0.04
2 -0.04
3
-0.08
-0.08
Current/A

2
Currnet/A

-0.12
1 -0.12
1
-0.16 0: blank
-5 -0.16 0: blank
1: 5× 10 M TBAB -5
-4 1: 5 ×10 M Pb(II)
-0.20 2: 10 M TBAB -0.20 -4
-3 2: 10 M Pb(II)
3: 10 M TBAB 0 -4
-0.24
3: 5 ×10 M Pb(II) 0
-0.24
0 1000 2000 3000 0 1000 2000 3000 4000
Time/sec Time/sec

Fig. 1. Current–time profile at a constant cathodic overpotential (−0.1 V) for elec- Fig. 2. Current–time profile at a constant cathodic overpotential (−0.1 V) for elec-
troplating Zn in a blank electrolyte (0.7 M ZnO + 8 M KOH + 20 g L−1 LiOH) with troplating Zn in a blank electrolyte (0.7 M ZnO + 8 M KOH + 20 g L−1 LiOH) with lead
tetrabutylammonium bromide (TBAB) as an additive under magnetic stirring. ion as an additive under magnetic stirring.
66 Y. Wen et al. / Electrochimica Acta 59 (2012) 64–68

Table 1
Cathodic current characteristics for deposits from electrolytes studied under an equal-charge (338 C) regime at the cathodic overpotential  = −100 mV.

Solution composition Time (min) Initial current (mA) Final current (mA) R = (FA − IA )/(FB − IB )

Blank solution 35 90.2 234 1.0

10−4 M Pb(II) 54 75.5 136.7 0.42
10−4 M TBAB 51 70.8 158.5 0.61
10−4 M Pb(II) + 5 × 10−4 M TBAB 60 80.8 114.2 0.23
10−4 M Pb(II) + 10−4 M TBAB 59 73.1 127.9 0.38

R, deposit ratio; FA , final current with additive; IA , initial current with additive; FB , final current in blank solution; and IB , initial current in blank solution.

0.00 and TBAB(R = 0.23–0.38) is much lower than that for the individual
addition of 10−4 M Pb(II) and TBAB (R = 0.42–0.61). There exists a
-0.05
trade-off between the charging time and the inhibition of spongy
-0.10 zinc growth. As can be seen, for the dual addition of 10−4 M Pb(II)
4
3 and 5 × 10−5 M TBAB, the deposit ratio is not only the lowest but
Current / A

-0.15 2 also the initial current is closed to that for the blank solution. Thus,
1 the dual addition of 10−4 M Pb(II) and 5 × 10−5 M TBAB would pro-
-0.20 0: blank
-4
duce the excellent performance for the deposited zinc anode.
1: 10 M TBAB The electrodeposited zinc surfaces at the cathodic overpotential
-0.25 -4
2: 10 M Pb(II)
-4 -4
 = −100 mV under magnetic stirring of electrolytes were exam-
3: 10 M Pb(II)+10 M TBAB
-0.30 -4 -5 0 ined by SEM. As shown in Fig. 4, an additive-free solution produces
4: 10 M Pb(II)+5×10 M TBAB
granular and spongy-like zinc deposits (Fig. 4a). The addition of
-0.35
additives in the solution causes the deposition morphologies of
0 1000 2000 3000 4000
zinc to be completely different. The addition of 10−4 M Pb(II)
Time / Sec
brings about a less open, relatively compact deposit with some
Fig. 3. Current–time profile at a constant cathodic overpotential (−0.1 V) for elec- pits and hollows(see Fig. 4b). The addition of 10−4 M Pb(II) and
troplating Zn in a blank electrolyte (0.7 M ZnO + 8 M KOH + 20 g L−1 LiOH) with lead 5 × 10−5 M TBAB produces a dense, smooth and compact deposit
ions and TBAB as additives under magnetic stirring. indicative of almost complete inhibition of spongy zinc growth (see
Fig. 4c).
the optimal concentration of 10−4 M. It suggests that the ability of
spongy zinc inhibition becomes stronger by mixed addition of lead 3.3. The influences of additives on the charge–diacharge
ions and TBAB. However, the inhibition effect is so large that the performance of zinc electrode
cathodic deposition current is reduced dramatically compared to
the initial current in the blank solution. The charging efficiency of Fig. 5 presents the charge–discharge efficiency versus cycle
the deposited zinc electrode will be low. When the concentration number of the test cells using either blank solution or that with the
of TBAB is decreased to 5 × 10−5 M, a more flattened current–time addition of 10−4 M Pb(II)and with the mixed addition of 10−4 M
curve can be observed. Moreover, the cathodic deposition current Pb(II) and 5 × 10−5 M TBAB tested at 20 mA cm−2 . From the pro-
is similar to the initial current in the blank solution. This shows files, cells using blank solution exhibit low coulombic and energy
that the growth of spongy zinc is greatly strained by joint addition efficiencies and a sharp drop when the cycle number of the cell is
of Pb(II) and TBAB in the electrolyte. Also, the charging efficiency beyond 34. With the addition of 10−4 M Pb(II), the cycling stability
of the deposited zinc electrode would be hardly influenced. of the cell is enhanced to a great extent. Substantially improved sta-
The current transients and deposit ratio taken from the bility is demonstrated by cells with the mixed addition of 10−4 M
current–time trials for a definite charge (338 C) are listed in Table 1. Pb(II) and 5 × 10−5 M TBAB. Further, with the addition of 10−4 M
The electro-deposition time and final current values are obtained Pb(II), there are two small drops on the cell efficiency and then it
for a defined charge of 338 C (the charge delivered from a blank recovered gradually to steady performance. With the mixed addi-
solution containing 10−4 M Pb(II) and 5 × 10−5 M TBAB over the tion of Pb(II) and TBAB, on the first cycle, the cell has a relatively low
60 min electrodeposition). The data from these tests indicate that charge–discharge efficiency. Subsequently, the charge–discharge
both additives exhibit superior performance to the blank solution. efficiency of the cell progressively increases and then it shows very
It can be found that the deposit ratio for the dual addition of Pb(II) steady performance starting from the fifth cycle.

Fig. 4. Zinc electrodeposit at  = −100 mV from the blank solution (a) and the alkaline solution containing 10−4 M Pb(II) (b) and the alkaline solution containing 10−4 M Pb(II)
and 5 × 10−5 M TBAB (c).
 Y. Wen et al. / Electrochimica Acta 59 (2012) 64–68 67

100
90
80
70

Efficiency / %
60
50
40
30
20 Current efficiency
10 (a) Energy efficiency
0
0 10 20 30 40 50
Cycle number

100 100
90 90
80 80
70
Efficiency / %

70

Efficiency / %
60 60
50 50
40 40
30 Current efficiency 30
Current efficiency
20 Energy efficiency 20 Energy efficiency
10 (b) 10 (c)
0 0
0 10 20 30 40 50 0 10 20 30 40 50
Cycle number Cycle number

Fig. 5. The charge–discharge efficiency vs. cycle number of test cells using (a) blank solution, (b) blank + 10−4 M Pb(II) and (c) blank + 10−4 M Pb(II) + 5 × 10−5 M TBAB; tested
at 20 mA cm−2 .

a 1.8 b 1.8
1.6
1.6
1.4
1.4
1.2
Voltage / V

1 3
Voltage / V

1.2
23 1.0
2
1.0 1
0.8 0.8
1- 10-4 MPb (II) 0.6
0.6 1- blanksolution
2- blank solution 0.4 -4
0.4 2 -10 MPb (II)
0.2 3- 10-4 MPb (II) + 5x 10-5 MTBAB 0.2 -4 -5
3 - 10 MPb (II) + 5×10 MTBA B
0.0 0.0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time / min Time / min

Fig. 6. The 25th discharge curves (a) and the 40th discharge curves (b) of the tested cells.

Fig. 6 shows the comparison of the 25th and 40th discharge  = −100 mV. The growth of spongy zinc is more greatly suppressed
curves of test cells. It can be seen that on the 25th cycle, few by the synergistic effect of lead and TBAB. A smooth and compact
differences on the discharge curves are observed except that with zinc deposit is obtained from the flowing electrolyte containing
the mixed addition of Pb(II) and TBAB the discharge voltage is a Pb(II) and TBAB. Highly improved rechargeability is achieved dur-
little bit higher than the other two curves. However, on the 40th ing charge–discharge cycling of cells by the mixed addition of
cycle, cells using additives exhibit higher discharge voltage than 10−4 M Pb(II) and 5 × 10−5 M TBAB into the blank solution. The
that of the blank electrolyte, especially for the dual addition of synergistic effect of Pb(II) and TBAB is further demonstrated.
Pb(II) and TBAB. The synergistic effect of Pb(II) and TBAB is further
demonstrated. Acknowledgement

4. Conclusions This work was financed by the National Basic Research Program
(973 Program) of China (2010CB227201).
The effectiveness of lead ions and TBAB as inhibitors of spongy
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