Journal of Power Sources 283 (2015) 300e304

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Journal of Power Sources

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Short communication

A tetradentate Ni(II) complex cation as a single redox couple for

non-aqueous flow batteries
Hyun-seung Kim a, Taeho Yoon a, Jihyun Jang a, Junyoung Mun a, b, Hosang Park a,
Ji Heon Ryu a, c, Seung M. Oh a, *
a
Department of Chemical and Biological Engineering, Seoul National University, Daehak-dong, Gwanak-gu, Seoul 151-742, Republic of Korea
b
Department of Energy and Chemical Engineering, Incheon National University, 12-1, Songdo-dong, Yeonsu-gu, Incheon 406-840, Republic of Korea
c
Graduate School of Knowledge-based Technology and Energy, Korea Polytechnic University, 2121 Jeongwang-dong, Siheung-si, Gyeonggi-do 429-793,
Republic of Korea

h i g h l i g h t s

Nickel(II)-1,4,8,11-tetraazacyclotetradecane is evaluated as a single redox couple for non-aqueous flow battery.

Ni(cyclam)[ClO4]2 shows a high solubility (0.4 M) in non-aqueous electrolyte.

Ni(cyclam)2þ offers a high working voltage (2.55 V) as a single redox couple.

Ni(cyclam)2þ is chemically and electrochemically stable.

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

Article history: Nickel(II)-1,4,8,11-tetraazacyclotetradecane is examined as a possible single redox couple for non-
Received 6 January 2015 aqueous flow batteries. The nickel complex cation is reduced at 1.81 V (vs. Fc/Fcþ) and oxidized at
Received in revised form 0.74 V, showing that this tetradentate Ni(II) complex cation can be used as a single redox couple that
13 February 2015
offers a cell voltage of 2.55 V. The maximum solubility is 0.4 M in 1.0 M tetraethylammonium tetra-
Accepted 16 February 2015
fluoroborate dissolved in a mixed solvent of ethylene carbonate and propylene carbonate. When tested in
Available online 19 February 2015
a non-flowing cell, this single redox couple exhibits a very stable cycle performance.
© 2015 Elsevier B.V. All rights reserved.
Keywords:
Redox-flow battery
Single redox couple
Metal complexes
Energy storage system
Non-aqueous electrolytes

1. Introduction electrochemical oxidation/reduction of redox couples on inert

electrodes. During charging, discharge-state redox couples, which
Recently, ever-increasing world energy consumption, coupled are dissolved in an electrolyte solution and stored in a reservoir, are
with the issue of global warming, has resulted in an increase in fed into the electrode chamber by pumping. During discharging,
research into energy storage systems (ESSs) [1,2]. Lithium-ion cells charge-state redox couples are pumped in a reverse manner. By
[1,3e6], sodium-ion cells [7e10], sodiumesulfur cells [11], and applying this operational principle, electricity storage capacity can
redox-flow batteries [12e16] have been proposed for use in ESSs. be adjusted by simply changing either the volume of the reservoir
Redox-flow batteries (RFBs) are considered reliable for application or the concentration of the dissolved redox couples. In addition,
in ESSs because of their unique operational principle; that is, electrode degradation in RFBs is insignificant because the redox
electric energy is stored and released into/from RFBs by reactions take place on an inert electrode surface, thus enabling
long cell life. This feature is in contrast to those in other candidates,
such as lithium-ion batteries in which the electrode material par-
ticipates in the redox reaction and thus vulnerable to degradation
* Corresponding author. [13,17].
E-mail address: [email protected] (S.M. Oh). Aqueous electrolyte RFBs have been developed [15e17];

http://dx.doi.org/10.1016/j.jpowsour.2015.02.083
0378-7753/© 2015 Elsevier B.V. All rights reserved.
 H.-s. Kim et al. / Journal of Power Sources 283 (2015) 300e304 301

however, the use of aqueous electrolytes restricts their application. 2. Experimental

Theoretically, the working voltage of these RFBs is limited to
<1.23 V because of water electrolysis. Moreover, their working 2.1. Synthesis
temperature is also limited to within a 0e100  C range [13,18,19].
These two constraints are removed when aqueous electrolytes are To prepare nickel(II)-1,4,8,11-tetraazacyclotetradecane perchlo-
replaced by non-aqueous ones; for instance, those based on the rate (Ni(cyclam)[ClO4]2), cyclam (Alfa Aesar, MA, USA; 98%) was
organic carbonate solvents. The carbonate-based non-aqueous added into an aqueous solution of nickel(II) perchlorate (Alfa Aesar;
electrolytes have a wider electrochemical stability window than reagent grade) [29]. A precipitate formed immediately, which was
that of aqueous ones, thereby allowing the working cell voltage to collected by filtration, and dried under vacuum at 80  C for 12 h
extend above 1.23 V, resulting in higher energy density. Moreover, before use.
propylene carbonate (PC), which is one of the common solvents
employed in lithium-ion cells and also used in this work as the 2.2. Cyclic voltammetry
solvent, shows a lower freezing (48.8  C) and higher boiling point
(242  C) as compared to those of water. Several redox couples have 0.01 M Ni(cyclam)[ClO4]2 was dissolved in 0.5 M tetraethy-
been reported for non-aqueous RFBs; metal-organic frameworks, lammonium tetrafluoroborate (TEABF4) that had been dissolved in
organic molecules and semi-solid systems [18e28]. However, a mixture of ethylene carbonate (EC) and propylene carbonate (PC)
almost of them show poor solubility (commonly <0.1 M) in non- (1:1, v/v; PANAX). Cyclic voltammetry was performed by using a
aqueous electrolytes [13]. Hence, highly soluble redox couples are glassy carbon working electrode (0.07 cm2), a silver wire quasi-
desperately needed to realize the advantage of non-aqueous RFBs. reference electrode, and a platinum counter electrode in an
In addition to the high solubility, the redox couples should meet argon-filled glove box. After cyclic voltammetry, ferrocene (Sigma
other requirements for practical use in RFBs. First, they should be Aldrich, MO, USA; 98%) was added into the solution to calibrate the
electrochemically and chemically stable. Otherwise, they decom- quasi-reference electrode [30]. In this study, the electrode potential
pose to form redox-inactive species, which results in a permanent was referenced to the ferrocene/ferrocenium (Fc/Fcþ) redox couple.
loss of redox couples and a decrease in cell capacity. Another
requirement for redox couples is high diffusion rate because the 2.3. Solubility
mass transfer, which affects the rate performance of the cells, is
decided by diffusion near the electrode surface. In summary, the 0.001 mol Ni(cyclam)[ClO4]2 was dissolved into 1.5 mL of 1.0 M
suitability requirements for redox couples for use in non-aqueous TEABF4/EC þ PC (1:1, v/v; PANAX). After stirring for 30 min at room
RFBs are: (i) high solubility for high capacity, (ii) high working temperature, the undissolved residue was removed by syringe filter
voltage for high energy density, (iii) high stability for long cell life, (Whatman, 25 mm, 1 mm). The filtrate was then analyzed by per-
and (iv) facile diffusion for high rate performance. forming inductively-coupled plasma atomic emission spectroscopy
The redox couples proposed to date can be classified into two (ICP-AES; OPTIMA 4300DV; PerkinElmer, MA, USA) at 167e782 nm
groups; dual and single redox couples [18,21,22]. In the dual sys- with argon plasma (6000 K).
tem, two different redox couples are utilized. For charging, one
redox couple is fed into the negative electrode chamber and the 2.4. Non-flowing cell test
other is fed into the positive chamber. Since two different redox
couples are separated by an ion-exchange membrane, the diffusion A non-flowing cell was fabricated by using a cation-exchange
of redox couples across the membrane is unavoidable due to the membrane (FuMA-Tech, Germany; fumapem® F-14100) and two
concentration difference between two chambers. Such a cross-over carbon papers (Toray Industries, Japan; TGP-H-60) as the inert
results in a permanent loss of redox couple in one chamber because electrode. Assessment of galvanostatic charge and discharge was
it can not return to its initial chamber. This will eventually lead to performed by using 0.01 M Ni(cyclam)[ClO4]2 dissolved in 1.0 M
capacity loss and distortion of the pre-designed negative/positive TEABF4/EC þ PC (1:1, v/v; PANAX) in an argon-filled glove box.
(N/P) capacity ratio of the RFB system. Another result of cross-over Before testing, the cation-exchange membrane was soaked for at
is the self-discharge of the charged redox couples. For instance, if least 12 h in the electrolyte solution. The charge and discharge
the oxidized redox couple in the positive electrode chamber moves currents were 0.3 C and 0.15 C, respectively.
to the negative electrode chamber across the membrane, it is
immediately reduced. This self-discharge should be avoided for the 2.5. Coin-cell test
RFBs for ESSs. The operational problems associated with the dual
system can be avoided by using a single redox couple system, in The galvanostatic charge and discharge assessment was also
which only one redox couple in the discharge-state is fed simul- conducted by using a coin-cell (two electrode, 2032 type), which
taneously into two chambers for charging. The charged (reduced or was fabricated by using the same cation-exchange membrane and
oxidized) species in each chamber are then converted into to the carbon paper. Before the test, the carbon paper and cation-
initial discharge-state upon discharging. In the single redox couple exchange membrane were wetted with 0.01 M Ni(cyclam)[ClO4]2
system, the self-discharge problem still exists because the charged dissolved in 1.0 M TEABF4/EC þ PC (1:1, v/v; PANAX) for 12 h. The
species can cross the separator. However, there is neither perma- charge and discharge current was fixed at 50 mA.
nent capacity loss nor distortion of N/P ratio because the self-
discharged species in both electrodes are being collected in the 3. Results and discussion
initial discharge-state.
In the present study, we assess a nickel (II) complex cation with Fig. 1a shows the molecular structure of Ni(cyclam)2þ, in which
a tetradentate ligand (1,4,8,11-tetraazacyclotetradecane; cyclam) the nickel(II) ion is chelated by four nitrogen atoms in cyclam [31].
for use as a single redox couple in a non-aqueous RFB. The goal of Maximum solubility of Ni(cyclam)[ClO4]2 at room temperature is
this study is to determine whether this metal complex cation sat- 0.4 M in 1.0 M TEABF4/EC þ PC mixed solvent (1:1, v/v), which is
isfies the above-mentioned four requirements. larger than that for the redox couples reported to date (<0.1 M) [13].
The oxidation and reduction behavior of Ni(cyclam)2þ is assessed
by using cyclic voltammetry. In a positive scan at a current density
302 H.-s. Kim et al. / Journal of Power Sources 283 (2015) 300e304

Fig. 1. (a) Molecular structure of Ni(cyclam)2þ and cyclic voltammograms of 0.01 M Ni(cyclam)[ClO4]2 in 0.5 M TEABF4 in EC/PC mixed solvent (1:1, v/v). (b) Ni(II) 4 Ni(III) and (c)
Ni(II) 4 Ni(I) redox reaction. The scan rates are indicated in the inset.

of 300 mV s1 (Fig. 1b), the initial Ni(II) complex cation is oxidized result is due to the ability of cyclam to stabilize the chelate struc-
to Ni(III) at 0.85 V (Epa vs. Fc/Fcþ), and the as-generated Ni(III) ture [31].
complex cation is reduced back to Ni(II) at 0.62 V (Epc vs. Fc/Fcþ). The cyclic voltammograms obtained from 0.4 M Ni(cyclam)
Note that the peak current density is similar for both oxidation and [ClO4]2 in 0.5 M TEABF4/EC þ PC are displayed in Fig. 3a and b. Note
reduction (ipa z ipc). In a negative scan at 300 mV s1 (Fig. 1c), the that the Ni(II) solution is the most concentrated one (0.4 M) at room
Ni(II) complex cation is reduced to Ni(I) at 1.90 V (Epc vs. Fc/Fcþ) temperature, such that the diffusion coefficient of Ni(II) complex
and re-oxidized back to Ni(II) at 1.71 V (Epa vs. Fc/Fcþ). cation is lowest. The diffusion coefficient of Ni(cyclam)2þ is calcu-
Fig. 2a shows cyclic voltammograms obtained at 2.1 V ~ þ1.5 V lated by using the scan-rate-dependent peak current values. In
(vs. Fc/Fcþ). The voltammogram traced with the background elec- Fig. 3a and b, the peak voltages (Ep) shift at faster scan rates, indi-
trolyte (1.0 M TEABF4/EC þ PC) shows that the given electrolyte is cating that the redox reactions are electrochemically irreversible.
electrochemically stable within the voltage range of þ2.0 V ~ 2.8 V For electrochemically irreversible redox reactions, the peak current
(vs. Fc/Fcþ). The two redox reactions of the Ni(II) complex (E1/ is expressed by the Randles-Sevcik equation (Equation (1)).
2 ¼ 0.74 V for Ni
2þ
4 Ni3þ þ e and 1.81 V for Ni2þ þ e 4 Niþ) take
place within the electrochemical stability window of the back- ip ¼ (2.99  105)n3/2a1/2AD1/2Cn1/2 (1)
ground electrolyte. Based on the two half-wave potentials, the
calculated cell voltage is 2.55 V. Note that this is twice larger than where a is calculated by using Equation (2) [32].
the maximum value (1.23 V) for aqueous electrolyte system. The
results shown in Fig. 2a illustrate that Ni(cyclam)2þ can be used as a jEp  Ep/2j ¼ 47.7/a mV at 25  C (2)
single redox couple in an RFB system. In such a system, the Ni(II)
complex is oxidized/reduced within the electrochemical stability The peak current values in Fig. 3a and b are plotted against the
window of the background electrolyte. In the charging process, the square-root of the scan rate as in Fig. 3c, from which the diffusion
Ni(II) complex cation, which is the discharged species, is oxidized to coefficients are calculated to be in the range 106e107 cm2 s1.
Ni(III) on the positive electrode and reduced to Ni(I) on the negative Based on the highly concentrated (0.4 M) redox couples in the given
electrode. The charged species (i.e., Ni(III) and Ni(I)) are restored non-aqueous electrolyte, these diffusion coefficient values are
back to the initial Ni(II) complex cation in the discharge process. reasonably high [18,19,33].
In Fig. 2b, the cyclic voltammogram recorded at the 50th scan Fig. 4a shows an accumulated capacityevoltage curve obtained
overlaps the trace obtained at the 1st scan. Obviously, the two from a non-flowing cell. At a charge level up to 30%, the majority of
voltammograms are similar in both peak shape and position, the charging takes place at 2.6e2.8 V, which is close to the cell
indicating that the electrochemically generated Ni(I) and Ni(III) voltage (2.55 V) that is expected from the cyclic voltammograms
complex cations are electrochemically and chemically stable in the shown in Fig. 2a. The results indicate that cell polarization is not
given electrolyte. If the Ni(I) and Ni(III) species are not stable, the severe in the charging process. However, a severe cell polarization
cyclic voltammograms would show new or distorted peaks. This is noticed in the discharge period; the major discharge reaction
 H.-s. Kim et al. / Journal of Power Sources 283 (2015) 300e304 303

Fig. 2. (a) Cyclic voltammograms encompassing Ni(II) 4 Ni(III) and Ni(II) 4 Ni(I)
redox reaction. The 1st and 50th voltammograms obtained at 300 mV s1 are over-
lapped in (b). The experimental condition was the same as for Fig. 1.

takes place near 1.0 V, which is far below the cell voltage. The
difference in cell polarization for charge and discharge seems to be
due to concentration overpotential. In the charging reaction, the
concentration of Ni(II) complex cation near the electrode surface is
so high (0.4 M) that the concentration polarization is negligible. In
the discharging reaction, however, the concentration of Ni(I) and
Ni(III) complex cation near the electrode surface is low since they
are diffused away from the electrode during the charging period.
Note that the electrode gap is 20.1 mm in this non-flowing cell. Fig. 3. Cyclic voltammograms obtained from 0.4 M Ni(cyclam)[ClO4]2 in 0.5 M TEABF4
Hence, a high concentration overpotential is expected in the in EC þ PC mixed solvent (1:1, v/v): (a) Ni(II) 4 Ni(III) and (b) Ni(II) 4 Ni(I) redox
reaction. (c) Peak current vs. scan rate1/2 plot for Ni(II) 4 Ni(I) and Ni(II) 4 Ni(III)
discharge process. To ascertain the prevalence of concentration redox reactions. The peak current values are derived from (a) and (b). The scan rates
overpotential, the charge/discharge reactions are performed in a are indicated in the inset.
coin-cell, in which the electrode gap is narrow enough (0.1 mm) to
ignore the diffuse-out phenomenon of the Ni(I) and Ni(III) complex
cations. As expected, the charge (2.6 V) and discharge (2.5 V) 4. Conclusion
voltages observed from the coin-cell are very close to the cell
voltage (2.55 V). That is, the concentration overpotential in the Ni(cyclam)2þ complex cation turns out to be suitable for use as a
discharge reaction is negligibly small. single redox couple in non-aqueous RFBs. The suitability is based on
Fig. 4c presents the discharge capacity profiles obtained by the following observations: (i) Ni(cyclam)[ClO4]2 has a maximum
cycling the non-flowing cell. The results show that the cell exhibits solubility of 0.4 M in 1.0 M TEABF4/EC þ PC; (ii) the cell voltage
a stable cycle performance, and the initial discharge capacity amounts to 2.55 V; (iii) Ni(cyclam)2þ complex cation is chemically
(0.08 mA h) is maintained until 30 cycles. This stable cycle per- and electrochemically stable; and (iv) the solution-phase diffusion
formance indicates that the degradation of Ni complex cations, rate is reasonably high. Also, a very stable cycle performance was
inert electrode, and electrolyte solution is insignificant. The high observed in a non-flowing cell. However, the performance results
stability is also evident in Fig. 4a, in which the charge/discharge presented in the present study are obtained from a non-flowing
voltage profiles obtained for 5 cycles are similar to each other. cell. Cycle stability and other cell performances should be tested
304 H.-s. Kim et al. / Journal of Power Sources 283 (2015) 300e304

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