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Journal of Power Sources 393 (2018) 32–36

Contents lists available at ScienceDirect

Journal of Power Sources


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

A chemically regenerative redox fuel cell using (2,2,6,6- T


tetramethylpiperidin-1-yl)oxyl redox reaction in acid medium
Sang-Beom Hana,b, Da-Hee Kwaka, Hyun Suk Parka, Jin-Young Parka, Kyeng-Bae Maa,
Ji-Eun Wona, Do-Hyoung Kima, Min-Cheol Kima, Kyung-Won Parka,∗
a
Department of Chemical Engineering, Soongsil University, Seoul 06978, Republic of Korea
b
BOYAZ Energy Inc., 218 Gurojoongang-ro, Guro-gu, Seoul 08212, Republic of Korea

H I GH L IG H T S G R A P H I C A L A B S T R A C T

• CRRFC was proposed using TEMPO


instead of O at the cathode.
2

• TEMPO showed fairly fast transport


and low activation energy for the re-
duction.
• CRRFC exhibited an open circuit vol-
tage of ∼0.7 V at 30 °C.
• CRRFC exhibited a maximum power
density of ∼90 mW cm −2
at 30 °C.

A R T I C LE I N FO A B S T R A C T

Keywords: (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) with no free radical and non-volatile characteristic can be
Chemically regenerative redox fuel cell utilized as a liquid catalyst instead of O2 at the cathode in a chemical regenerative redox fuel cell with H2 as a
Cathode fuel at the anode. In this study, the electrochemical properties and performance of TEMPO dissolved in sulfuric
TEMPO acid solution are investigated using half and unit cells. In the half-cell, TEMPO shows an activation energy of
Redox reaction
1.27 kcal mol−1 K−1 for the reduction. A chemical regenerative redox fuel cell (CRRFC) using TEMPO as the
liquid catalyst exhibits an open circuit voltage of 0.7 V and a maximum power density of 90 mW cm−2 at 30 °C
with a low activation loss. The regeneration cycling test of the CRRFC is performed at a constant voltage of 0.4 V
under a flow rate of the oxygen-bubbled TEMPO solution. The performance of the CRRFC deteriorates, i.e., a
power density of zero measured at > 200 min. Thus, a highly efficient regeneration system needs to be devel-
oped for a high-performance CRRFC using TEMPO used as a liquid-type oxidant. Furthermore, stable liquid
oxidants with relatively high standard reduction potentials can be proposed through various organic compounds.

1. Introduction can be used to oxidize alcohol to aldehyde or aldehyde to carboxyl and


can be continuously regenerated via the reoxidation process of the re-
(2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) with a chemical duced TEMPO by oxygen [6–10], with no byproduct formation. Re-
formula of (CH2)3(CMe2)2NO is a chemical compound with a fairly cently, it has been used in electrochemical reactions, involving ionic
stable radical, as proposed by Lebedev and Kazarnowskii in 1960's [1]. species and electrons as well as organic chemical process. Janoschka
It has been used as mediators for radical maker, organic synthesis, and and Wang et al. reported a redox flow battery using TEMPO-based
radical polymerization [2–5]. For example, TEMPO as an anode catalyst catholyte as an energy storage device with high-energy density and


Corresponding author.
E-mail address: kwpark@ssu.ac.kr (K.-W. Park).

https://doi.org/10.1016/j.jpowsour.2018.05.009
Received 5 January 2018; Received in revised form 30 April 2018; Accepted 2 May 2018
0378-7753/ © 2018 Elsevier B.V. All rights reserved.
S.-B. Han et al. Journal of Power Sources 393 (2018) 32–36

2.2. Electrochemical reduction reaction of TEMPO in an acid medium

The electrochemical reduction reaction of TEMPO was character-


ized in a three-electrode electrochemical cell. A glassy carbon (GC), Pt
wire, and Ag/AgCl were used as the working, counter, and reference
electrodes, respectively. Linear sweep voltammograms (LSVs) of
TEMPO were obtained using a GC rotating disk electrode (RDE) with
varying rotating speeds in N2-saturated 1 M H2SO4 + 0.1 M TEMPO at
25 °C. The electrochemical reduction properties of TEMPO were char-
acterized using a GC electrode in N2-saturated 1 M H2SO4 + 0.1 M
TEMPO at different reaction temperatures (30, 40, 50, and 60 °C).

2.3. Unit cell measurement

The membrane-electrode-assembly (MEA) for the CRRFC using


TEMPO was fabricated by hot-pressing Nafion® 212 and Pt/C (0.1
Fig. 1. The disproportionation and redox potential of TEMPO.
mgPtcm−2, E-TEK) with an area of 5 cm2 as an anode at 110 °C under a
pressure of 50 bar for 2 min. The as-prepared NCF electrode was used as
high efficiency [11,12]. the cathode. A monopolar plate with a serpentine channel was utilized
A chemical regenerative redox fuel cell (CRRFC) is an alternative of for the anode whereas the plate with a plate-shape (3 mm in depth) was
polymer electrolyte membrane fuel cells (PEMFCs) used as solid-state used as the cathode. The unit cell measurement for the CRRFC with the
non-precious metal catalysts for oxygen reduction reaction (ORR) fabricated MEA was performed using a computer-controlled fuel cell
[13–16]. The precious metals for cathode catalysts in PEMFCs have station (CNL Energy, Korea) at 30 °C. Hydrogen gas with a relative
been mainly utilized because of their electrocatalytic activity for humidity of 100% at 30 °C, was supplied at the anode at a flow rate of
oxygen, stability in acidic media, and high electrical conductivity 30 mL min−1. At the cathode, the 100 mL solution containing 0.3 M
[17–22]. Instead of the solid-state metal catalysts for ORR, liquid cat- TEMPO and 1 M H2SO4 was supplied under a flow rate of 2 mL min−1.
alysts such as TEMPO might be applied to the CRRFC with the redox The stability test of the CRRFC was performed at a constant voltage of
reaction of the liquid catalysts. Thus, the reduced liquid catalysts at the 0.4 V for 200 min.
cathode in the CRRFC can be chemically re-oxidized or regenerated by
O2 gas [22]. In the previous study, several liquid catalysts have been 3. Results and discussion
proposed for high-performance CRRFCs [23–25]. Herein, TEMPO with
no free radical and non-volatile characteristic was firstly utilized as the Fig. 2 shows a schematic illustration of a CRRFC using TEMPO
liquid catalyst instead of O2 at the cathode in the CRRFC with H2 as the chemically oxidized by O2 (TEMPO+) as the liquid catalyst (denoted as
fuel at the anode. CRRFC-TEMPO). At the anode in the CRRFC-TEMPO, H2 as the fuel is
In particular, TEMPO with a standard reduction potential of electrochemically oxidized on a Pt/C catalyst (Eq. (3); namely “Hy-
∼0.76 V (Fig. 1(a)) dissolved in 1 M H2SO4 was used as a liquid-type drogen Oxidation Reaction (HOR)” with the same structure as that of
oxidant at the cathode [26–29]. TEMPO used as the liquid catalyst in typical proton exchange membrane fuel cells (PEMFCs) using O2 as an
CRRFC can be chemically oxidized to TEMPO+ by O2 (Eq. (1)). The oxidant supplied at the cathode. The proton (H+) and electron pro-
oxidation reaction of TEMPO is also known as the regeneration reaction duced by the HOR at the anode transport to the cathode and are elec-
for TEMPO+ as a liquid catalyst [30,31]. The oxidized liquid catalyst trochemically reduced with TEMPO+ as a liquid catalyst at a reduction
(TEMPO+) acting as an oxidant, supplied at the cathode instead of O2, potential of 0.76 V (Eq. (2)). The theoretical cell potential of the
can be electrochemically reduced to TEMPO on carbon felt electrode, CRRFC-TEMPO, the difference between the HOR (0 V) and the reduc-
consuming electrons (Eq. (2)). Furthermore, H2 supplied at the anode in tion of TEMPO (0.76 V), by the total electrochemical reaction (Eq. (4))
the CRRFC can be electrochemically oxidized (Eq. (3)). The overall is 0.76 V.
reaction in the CRRFC with the oxidation of H2 as a fuel at the anode The electrochemical properties of TEMPO in an acid medium, the
and a reduction of TEMPO as a liquid catalyst at the cathode together CV and LSVs were investigated by cyclic voltammetry (CV) and LSV on
with the regeneration reaction of Eq. (1) can be expressed by Eq. (4). a GC in N2-saturated 0.1 M TEMPO + 1 M H2SO4 (Fig. 3). The
O2 + 4TEMPO + 4H+ → 4TEMPO+ +2H2O (1)

4TEMPO+ + 4e− + 4H+ → 4TEMPO + 4H+ (2)

2H2 → 4H+ + 4e− (3)

2H2 + O2 → 2H2O + Electric energy (4)

2. Experimental

2.1. Synthesis of N-doped carbon felt (NCF)

The nitrogen-doped carbon felt electrode used as the cathode was


prepared by heating a carbon felt with a volume of
2.24 × 2.24 × 0.65 cm3 (SQ 10001, CeTech Co. Ltd) under an NH3
atmosphere at 700 °C for 3 h. Fig. 2. A schematic illustration of the CRRFC operated using TEMPO+ as the
liquid catalyst at the cathode connected with a chemical regeneration system by
O2 and H2 as the fuel at the anode.

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S.-B. Han et al. Journal of Power Sources 393 (2018) 32–36

Fig. 3. CV and LSVs were measured on a GC as a working electrode in N2-


saturated 0.1 M TEMPO + 1 M H2SO4.

oxidation and reduction reactions of TEMPO were characterized using


CV as shown in Fig. 3(a). In general, the disproportionation can occur
when the reduction potential of the reduction is significantly lower than
that of the oxidation potential. Since the potential difference in the case
of TEMPO is > 0.7 V, as shown in Fig. 1, TEMPO dissolved in an
electrolyte can exhibit the disproportionation containing both TEMPO+
and TEMP-OH. Thus, in the CV, the positive and negative current
density values according to the applied potentials result from the oxi-
dation and reduction reactions of TEMPO, respectively. Furthermore,
the oxidation peak potential of TEMPO to TEMPO+ at 0.73 V with in-
creasing potential and the reduction peak potential of TEMPO+ to
TEMPO at 0.68 V with decreasing potential were obviously observed.
The close values of the oxidation and reduction potentials on the GC
demonstrate the reversible redox reaction, i.e. reduction of TEMPO+ to
TEMPO and oxidation of TEMPO to TEMPO+, on a nonprecious metal
(NPM) catalyst. To further identify the electrochemical reduction re-
action of TEMPO in an acid medium, LSVs were obtained in N2-satu-
rated 0.1 M TEMPO + 1 M H2SO4 using an RDE with varying rotating
speeds from 100 to 2500 rpm (Fig. 3(b)). The reduction current den-
sities, observed from ∼0.8 V vs. NHE, increased because of a faster Fig. 4. (a) Levich and (b) Koutecký−Levich plots measured using the curves of
velocity for mass transport with increasing rotating speed. the reduction current as a function of rotating speed. (c) A plot of kinetic
The Levich and Koutecký-Levich plots measured using the curves of current versus potential.
the reduction current as a function of rotating speed are shown in
Fig. 4(a) and (b), respectively. Using the slope of the Levich plot 2 1 −1
(Fig. 4(a)), the diffusion coefficient of TEMPO in an acid medium were IL = (0.620)nFAD 3 w 2 v 6 C (5)
determined as 4.75 × 10−6 cm2 s−1 by using the following equation: where IL, n, F, A, D, ω, ν, and C are the current density, electron
number, Faraday constant, active area, diffusion coefficient, angular

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S.-B. Han et al. Journal of Power Sources 393 (2018) 32–36

Fig. 6. Polarization curve of the CRRFC measured using TEMPO+ as the oxi-
dant and H2 as the fuel at 30 °C. The humidified H2 and the solution containing
0.3 M TEMPO and 1 M H2SO4 were supplied at the anode and cathode in the
CRRFC, respectively.

The unit cell measurement using TEMPO as an oxidant and H2 as a


fuel was performed at 30 °C. The humidified H2 and the solution con-
taining 0.3 M TEMPO and 1 M H2SO4 were supplied at the anode and
cathode in the CRRFC, respectively. In particular, the TMEPO solution
was recycled by bubbling pure O2 gas and circulated to the cathode.
Since TEMPO can be oxidized and reduced at the same time due to the
disproportionation of TEMPO, the CRRFC exhibited a relatively low
open circuit voltage (OCV) of 0.7 V instead of a high OCV of 1.2–1.5 V,
whereas the CRRFC showed a maximum power density of 90 mW cm−2
with a low activation loss despite the low cell temperature of 30 °C
(Fig. 6). The regeneration cycling test in the CRRFC was investigated at
a constant voltage of 0.4 V under a flow rate of the oxygen-bubbled
TEMPO solution. As shown in Fig. 7, the cell performance of CRRFCs
using TEMPO+ (yellow color) used as the liquid catalyst instead of O2
gradually deteriorated. The decreased performance in the CRRFC, i.e. a
power density of zero measured at > 200 min, might be attributed to
Fig. 5. (a) Current−voltage curves of the reduction TEMPO with varying re- the favorable generation of thermodynamically stable TEMPO-OH and
action temperature in N2-saturated 0.1 M TEMPO + 1 M H2SO4. (b) The relatively low regeneration efficiency of TEMPO to TEMPO+ used as an
Arrhenius plot of ln(j) vs. 1/T obtained using the current values measured at oxidant under the present conditions. In addition, the yellow color
0.6 V. TEMPO solution turned transparent during the regeneration test, de-
monstrating the partial conversion of TEMPO to TEMPO-OH. The cell
velocity, kinematic viscosity, and concentration, respectively. The dif- performance of CRRFCs gradually deteriorated due to the favorable
fusion coefficient value of TEMPO with a molecular weight of
156.25 g mol−1 is similar to those of small molecules such as methanol
(32 g mol−1; 1.28 × 10−5 cm2 s−1) and ethanol (46 g mol−1;
1.24 × 10−5 cm2 s−1), indicating the fairly fast transport of TEMPO
[32]. In the Koutecký-Levich plots (Fig. 4(b)), the independent and
dependent variables are (rotating rate)−1/2 and (current)−1 measured
at each voltage, respectively. The intercept at the y-axis is the current
measured at an infinite velocity of the rotating disc electrode (RDE),
namely the kinetic current is independent of the mass transport. The
kinetic currents were determined as a function of potential, as shown in
Fig. 4(c), demonstrating the maximum current under the sufficiently
fast mass transport. The electrochemical reduction properties with
varying reaction temperature using a GC in N2-saturated 0.1 M TEMPO
+ 1 M H2SO4 are shown in Fig. 5(a). With increasing temperature from
30 to 60 °C, the reduction current densities (j) increased. The Arrhenius
plot of ln(j) vs. 1/T was obtained using the current values measured at
0.6 V with varying reaction temperature (Fig. 5(b)). From the slope of
the plot, the apparent activation energy for the reduction reaction of
TEMPO was determined as 1.27 kcal mol−1 K−1, demonstrating that
TEMPO can be a superior oxidant with extremely low activation energy Fig. 7. Regeneration cycling test of the CRRFC (unit cell) connected to a re-
on a NPM catalyst, compared to ∼40 kcal mol−1K−1 for the ORR on a generation system. The inset represents the photo image of the TEMPO in
Pt catalyst. 1 M H2SO4 (left) and the solution after the regeneration cycling test (right).

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S.-B. Han et al. Journal of Power Sources 393 (2018) 32–36

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