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Contents lists available at ScienceDirect

Journal of Industrial and Engineering Chemistry

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

Enhanced cycle stability of rechargeable Li-O2 batteries using

immobilized redox mediator on air cathode
Ji-Hoon Baika,1, Su Young Leea,b,1, Kihyun Kimc, Seongjun Baea,b , Sangwan Kima ,
Soyoul Kwakd, Dong Gi Honga , Inho Namd,* , Jongheop Yia,b,* , Jong-Chan Leea,*
a
School of Chemical and Biological Engineering and Institute of Chemical Processes, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul, 08826,
Republic of Korea
b
WCU Program of C2E2, ICP, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul, 08826, Republic of Korea
c
School of Materials Science and Engineering Polymer Science and Engineering, Gyeongsang National University, 501 Jinju-daero, Jinju, 660-701, Republic of
Korea
d
School of Chemical Engineering & Materials Science, Institute of Energy Converting Soft Materials, Chung-Ang University, 84 Heukseok-ro, Dongjak-gu,
Seoul, 06974, Republic of Korea

A R T I C L E I N F O A B S T R A C T

Article history: Overcoming the low round-trip energy efficiency and poor cycle stability of lithium-oxygen (Li-O2)
Received 3 July 2019 batteries still remains a challenge. Here, we show that 2,2,6,6,-tetramethylpiperidinyl-1-oxyl (TEMPO)-
Received in revised form 15 October 2019 immobilized air cathode can effectively reduce the charge voltage and increase the cycle stability in Li-O2
Accepted 10 November 2019
batteries. The TEMPO-immobilized air cathode is prepared using a gas diffusion layer by a simple dip
Available online xxx
coating method, in which polydopamine is used as a linker. In this method, the immobilized TEMPO on
the cathode does not crossover to the anode, and the consumption of TEMPO by side reactions is
Keywords:
minimized. As a result, the redox mediation by TEMPO is well maintained in its immobilized state. This
Lithium-oxygen batteries
Redox mediator
highlights that the use of an immobilized redox mediator can be a rational strategy for expanding the
2,2,6,6,-tetramethylpiperidinyl-1-oxyl practical applications of Li-O2 batteries.
Polydopamine © 2019 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
Modified air cathode reserved.

Introduction such as the oxidative decomposition of the cathode during the

Aprotic lithium-oxygen (Li-O2) batteries have recently attracted
significant interests because of their high theoretical specific
energy of up to 13,000 Wh kg
1, which overcomes the limitation of
intercalation electrodes [1–5]. However, the practical application
of Li-O2 batteries requires overcoming several challenges such as
the low round-trip energy efficiency and poor cycle stability [6,7].
Since insoluble and insulating polycrystalline lithium peroxide
(Li2O2) is formed on the cathode surface during the discharge
process, a high overpotential is required in the charging process to
reduce Li2O2, leading to the extremely low round-trip efficiency
[8–10]. Carbonaceous materials with high electric conductivity,
light weight, and low fabrication cost have been used for cathodes
of Li-O2 batteries. However, they are prone to parasitic reactions
* Corresponding authors.
E-mail addresses: inhonam@cau.ac.kr (I. Nam), jyi@snu.ac.kr (J. Yi),
jongchan@snu.ac.kr (J.-C. Lee).
1
J.-H.B. and S.Y.L. contributed equally.
charging process at high potentials [11]. The decomposed products
block the surface of the carbon cathode, and this is considered as
the major reason for the poor cycle stability [7]. Therefore,
reduction of the overpotential during charging is essential for the
application of Li-O2 batteries, because it can provide higher energy
efficiency and long term cycle stability.
Heterogeneous catalysts including nanoparticles and metal
oxides have been widely used to reduce the charge overpotential in
Li-O2 batteries [12–15]. A redox mediator (RM) is used by
dissolving it in the electrolyte, as the former can act as electron
carriers between the electrode surface and Li2O2 via the reversible
reaction such as RM Ð RM+ + e
[16–18]. However, dissolution of
the RM in the electrolyte results in the diffusion through the
separator and reduction at the Li anode. As the RM is consumed
during the electrochemical process, the redox mediation is not
possible anymore [19]. Hence, the strategy of dissolving the RM in
the electrolytes has a certain disadvantage. Several approaches
using size-exclusive separators [20,21], negatively charged sepa-
rators [22], and gel polymer electrolytes [23] have been tried to
address the undesirable consumption of RM. However, no clear

https://doi.org/10.1016/j.jiec.2019.11.015
1226-086X/© 2019 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.

Please cite this article in press as: J.-H. Baik, et al., Enhanced cycle stability of rechargeable Li-O2 batteries using immobilized redox mediator on
air cathode, J. Ind. Eng. Chem. (2019), https://doi.org/10.1016/j.jiec.2019.11.015
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solutions have been arrived at as yet, primarily because of the self-
discharge process, which is an inherent disadvantage in the current
configurations of Li–O2 batteries.
In this study, we tried to immobilize the RM on a gas diffusion
layer (GDL) cathode to prevent its diffusion to the Li metal anode.
Polydopamine (PDA), a mussel-inspired functional material, was
used as a linker to connect the RM to GDL, because PDA can be
easily coated on various substrates [24,25] and has a catechol
group that can react with the amino group in RM via Michael
addition or Schiff base formation [26,27]. As 2,2,6,6,-tetramethyl-
piperidinyl-1-oxyl (TEMPO) and its derivatives have been applied
as mobile RM in Li-O2 batteries owing to their appropriate redox
potential, fast electrochemical kinetic, good redox reversibility,
and high solubility in aprotic electrolytes [16,28,29], 4-amino-
2,2,6,6,-tetramethylpiperidinyl-1-oxyl (4-amino-TEMPO) was
used as the RM for immobilization. TEMPO-attached graphene
oxide has been used as a heterocatalyst for the oxidation of
alcohols to aldehydes or ketones, demonstrating that the
immobilized TEMPO can still participate in redox reactions
[30,31]. Breton et al. reported that TEMPO-attached electrode
exhibited electrocatalytic activity [32,33]; however, there are no
report on immobilized RM on the cathode of Li-O2 batteries. The
Li-O2 battery prepared using our modified air cathode exhibited an
enhanced cycle stability with reduced charge overpotential,
compared with those of the conventional Li-O2 batteries without
any RM or with RM dissolved in electrolyte.
Experimental
TEMPO-immobilized cathode was prepared using the gas
diffusion layer (GDL, JNT-20A, JNTG) as a carbon cathode and
substrate on which the PDA layer was coated. The GDL was cut into
3 cm  3 cm pieces and washed with ethanol. The GDL was
immersed in 20 mM precursor solution (dopamine hydrochloride,
Sigma Aldrich) while maintaining the pH at 8.5 in 20 mM Tris
buffer and then stirring for 30 min. The GDL treated with PDA was
immersed overnight in 20 mM TEMPO-precursor solution (4-
amino-2,2,6,6-tetramethylpiperidine 1-oxyl, TCI chemicals) while
maintaining the pH at 7.8 in 50 mM Tris buffer to induce Schiff base
formation or Michael addition between 4-amino-2,2,6,6-tetrame-
thylpiperidine 1-oxyl and the catechol group of PDA.
The modified GDL was used as a cathode in a Li-O2 battery
assembled in the Swagelok-type cell with lithium metal as an
anode and tetraethylene glycol dimethyl ether (TEGDME, Sigma-
Aldrich) containing 1 M lithium bis(trifluoromethanesulfonyl)
imide (LiTFSI, Sigma-Aldrich) as the electrolyte. TEGDME was
dried over molecular sieves (3 Å) prior to use. All the batteries were
assembled in an argon-filled glove box, and 100 mL of electrolyte
was used. The batteries were transferred to a homemade closed
chamber to purge oxygen for 1 h before the electrochemical
characterizations. Galvanostatic charge-discharge test and linear
sweep voltammetry (LSV) test were conducted with a multichan-
nel automatic battery cycler (WonATech, WBCS3000) at 30  C. The
current density and scan rate for the electrochemical analyses
were 0.1 mA cm
2 and 1 mV s
1, respectively. The voltage was
Fig. 1. Schematic of the construction of cathode with immobilized TEMPO.
Please cite this article in press as: J.-H. Baik, et al., Enhanced cycle stability of rechargeable Li-O2 batteries using immobilized redox mediator on
air cathode, J. Ind. Eng. Chem. (2019), https://doi.org/10.1016/j.jiec.2019.11.015
varied from 2.2 to 4.7 V, and the charge-discharge cycles were
investigated at a fixed capacity of 0.5 mA h cm
2 to minimize the
contribution from parasitic reactions. The surface elemental
composition was determined by X-ray photoelectron spectroscopy
(XPS, Thermo Scientific, Sigma Probe). The binding energy was
corrected with reference to the C 1s peak at 284.5 eV.
Density functional theory (DFT) calculations were carried out
with the Vienna ab initio simulation package (VASP) [34]. The
generalized gradient approximation Perdew-Burke-Ernzerhof
(GGA-PBE) exchange-correlation functional was applied to the
calculation, and the projector augmented wave (PAW) method, as
implemented in VASP, was employed [35–37]. A plane-wave
energy cutoff of 400 eV and 1 1 1 Monkhorst-Pack k-point mesh
were employed to sample the Brillouin zone. The Van der Waals
interactions between the organic molecules were also considered
using a DFT-D2 method established by Grimme. Grimme’s
parameters were sourced from the previous work by Kresse
[34]. The difference in the charge density, Dr, of TEMPO before and
after binding with PDA is defined as
Dr ¼ rPDA=TEMPO
ðrPDA þ rTEMPOÞ
where r is the charge density of the molecular unit denoted in
subscript.
Results and discussion
The GDL was readily functionalized via the consecutive coating
by dopamine and grafting of TEMPO onto the PDA layer, as shown
in Fig. 1. When dopamine hydrochloride was added into a weak
alkaline buffer solution (pH 8.5), dopamine was immediately
coated on the surface by oxidative polymerization, changing the
color of the solution from colorless to brownish black. The self-
polymerization of dopamine produces an adhesive coating layer of
PDA onto the GDL cathode. 4-Amino TEMPO was grafted onto the
PDA-coated GDL cathode via Michael addition or Schiff’s base
reaction. Considering that Schiff-base formation is facilitated in
weak acid condition, the product through Michael addition is
expected to be dominant in the immobilized TEMPO on cathode.
Since these chemical reactions can occur by simply dipping in
aqueous solutions, the GDL could be functionalized without any
complex procedures or harsh treatment, which is advantageous for
commercialization and mass production. Multifunctional electro-
chemical platforms can also be prepared in a similar manner using
other compounds having amino, thiol, and imidazole functional
groups, which can react with catechol groups in the PDA coated on
the GDL [38,39].
The successful functionalization and grafting were confirmed
by LSV from an open circuit voltage to 4.8 V (vs. Li/Li+) using the
Li-O2 battery containing the modified cathode (Fig. 2). As a control
system to observe the effect of the immobilized RM, another Li-O2
battery was prepared, where TEMPO was simply dissolved in the
electrolyte (10 mM TEMPO and 1 M LiTFSI in TEGDME), rather than
being immobilized. The LSV of the control system was performed.
An appropriate RM in Li-O2 batteries should have a redox potential
greater than that for the formation of Li2O2 (2.96 V vs. Li/Li+). The
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LSV curve of the Li-O2 battery with TEMPO dissolved in the

Fig. 2. Linear sweep voltammograms of the Li-O2 batteries with TEMPO dissolved
in the electrolyte and immobilized TEMPO on the cathode. Scan rate is 1 mV s
1.
electrolyte shows an anodic peak at 3.76 V (vs. Li/Li+), representing
the electrochemical oxidation of TEMPO to TEMPO+. On the other
hand, the Li-O2 battery with the immobilized TEMPO on cathode
shows slightly larger anodic peak potential of 3.93 V (vs. Li/Li+),
because the dangled structure can change the electron density of
the reaction site toward an electronically depleted state. The
amount of immobilized TEMPO on the cathode was estimated from
the area of the anodic peak for TEMPO/TEMPO+ redox couple
(Fig. 2). The area of the anodic peak for TEMPO dissolved in the
electrolyte (A1) and that for immobilized TEMPO on the cathode
(A2) were 0.0397 and 0.0315 C, respectively. Thus, the amounts of
TEMPO dissolved in the electrolyte and immobilized TEMPO on the
cathode are calculated to be 0.411 and 0.326 mmol/cell, respec-
tively. It is noteworthy that the loaded TEMPO in the cell in which
TEMPO was dissolved in the electrolyte was 1 mmol/cell, indicating
that the dissolved TEMPO easily decomposed via the reaction with
the lithium metal anode. The ratio of A1/A2 is 1.26, suggesting that
the amount of immobilized TEMPO on the cathode is slightly
smaller than that of the active TEMPO dissolved in the electrolyte.
The Li-O2 battery with immobilized TEMPO on cathode exhibited

Fig. 3. Model structures obtained by the (a) Michael addition reaction and (c) Schiff-base formation of dopamine and TEMPO and (b, d) their corresponding plots of charge
density difference obtained by DFT calculation (For interpretation of the references to color in the text, the reader is referred to the web version of this article).

Please cite this article in press as: J.-H. Baik, et al., Enhanced cycle stability of rechargeable Li-O2 batteries using immobilized redox mediator on
air cathode, J. Ind. Eng. Chem. (2019), https://doi.org/10.1016/j.jiec.2019.11.015
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Fig. 4. (a) N 1 s peak in the XPS spectra of bare cathode, PDA-coated cathode, and TEMPO-immobilized cathode. Magnified N 1 s peak of (b) PDA-coated cathode and (c)
TEMPO-immobilized cathode.

better cycle stability as compared with the case where TEMPO
was dissolved in the electrolyte (discussed later). Therefore, it can
be concluded that the RM is more effectively utilized in its
immobilized state, and this immobilization strategy can guide the
designing principles for electrodes of batteries containing RMs.
The energy difference between the dissolved and immobilized
TEMPO was estimated using density functional theory (DFT)
calculations. 4-Amino-TEMPO bonded to dopamine via Michael
addition and Schiff-base formation at the ortho-position were
chosen as the model structure (Fig. 3(a), (c)), and their charge
density was compared with that of the unbound TEMPO and
dopamine. The hydrogen atom of TEMPO has been hidden for
easier visualization. The plots of the calculated charge density
difference are shown in Fig. 3(b) and (d); blue and yellow lobes

Fig. 5. Cycle stability of Li-O2 batteries (a) with TEMPO dissolved in the electrolyte, (b) with immobilized TEMPO on the cathode, (c) without TEMPO, and (d) with PDA-coated
cathode. Charge-discharge profiles of the 1st, 5th, 10th, and 20th cycles. (e) Round-trip efficiency of the Li-O2 batteries with TEMPO. (f) Full discharge profiles up to 2.2 V (vs. Li/
Li+) of the all prepared Li-O2 batteries. Current density is 0.1 mA cm–2.

Please cite this article in press as: J.-H. Baik, et al., Enhanced cycle stability of rechargeable Li-O2 batteries using immobilized redox mediator on
air cathode, J. Ind. Eng. Chem. (2019), https://doi.org/10.1016/j.jiec.2019.11.015
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represent the charge depletion and accumulation after bonding,
respectively. It is remarkable that the charge depletion occurs at
N

O bond of TEMPO (red arrows) when TEMPO is bonded to
dopamine in the both cases. This could be attributed to the
increased electron-withdrawing effect of the nitrogen atom in 4-
amino TEMPO after bonding, in which the formal charge is partially
positive. After TEMPO loses an electron in the charging process,
N

O becomes N+¼O having a double-bond character and positive
charge on the nitrogen atom [16]. The charge depletion on N and O
atoms in the N

O bond indicates that TEMPO bonded to PDA are
partially oxidized, which would resist the additional electron loss
during the charge process, resulting in the positive shift of the
charge plateau. The immobilized TEMPO was also examined by XPS
(Fig. 4). For PDA-coated cathode, the binding energy was found to
be 400.1 eV, which corresponds to the nitrogen from PDA. For the
TEMPO-immobilized cathode, the binding energies were 400.1 and
402.2 eV, which correspond to a nitrogen atom from PDA and an
amino group from 4-amino-TEMPO and the nitroxide nitrogen
atom in the TEMPO, respectively. It is to be noted that no high
binding energy N 1s peak at 405 eV was observed. These results
suggest that 4-amino-TEMPO was directly bound to PDA via
covalent bonding rather than physical adsorption [40]. This is in
good agreement with the computational simulations and electro-
chemical analyses.
The electrochemical performances of the Li-O2 batteries without
any RM, with TEMPO dissolved in the electrolyte, and with
immobilized TEMPO on the cathode were evaluated via the
galvanostatic discharge/charge test (Fig. 5). As a conventional Li-
O2 battery setup, a Swagelok cell with Li metal anode and a fully
sealed gas reservoir were fabricated to enable high reproducibility.
Fig. 5 shows that the discharge plateaus appear at approximately
2.7 V for the all the fabricated Li-O2 batteries, demonstrating that
the discharge reaction is not affected by TEMPO. However, the
charging voltage in the first cycle significantly decreases in the
presence of TEMPO, as observed from the LSV data, resulting in a
significant improvement of the round-trip efficiency. In the first
cycle, the battery with TEMPO dissolved in the electrolyte shows a
plateau-like charging curve at 3.6–3.7 V (vs. Li/Li+) (Fig. 5(a)) and the
battery with immobilized TEMPO on the cathode shows the same at
3.8–3.9 V (vs. Li/Li+) (Fig. 5(b)). This is attributed to the electro-
chemical oxidation of TEMPO to TEMPO+, which is shown in the
voltammogram from linear sweep voltammetry (Fig. 2). It is
noteworthy that both the dissolved and immobilized TEMPO can
successfully act as RMs, because the charge voltage of these
batteries are evidently smaller than those of the batteries without
TEMPO containing both the bare cathode and the PDA coated
cathode without TEMPO (4.1 V) (Fig. 5(c–d)). The charge capacity of
the battery without TEMPO did not reach to 0.5 mA h cm
2 at 4.7 V in
the 20th cycle due to the increased charge overpotential,
demonstrating the unstable battery operation. For the battery with
TEMPO dissolved in the electrolyte, a rapid increase in the charging
voltage is observed immediately after the first cycle. This can be
ascribed to the parasitic degradation reactions that may lead to the
depletion of RM, resulting in electrode passivation and increased
polarization during cycling. In contrast, much lesser change in the
charging voltage is observed over 20 cycles for the battery with
immobilized TEMPO on the cathode. The improved cycle stability in
this case can be mainly attributed to the increased lifetime of TEMPO
on the cathode. Consequently, the stable round-trip efficiency over
cycles is achieved in the battery with immobilized TEMPO on
cathode. (Fig. 5(e)) The full discharge capacities of the Li-O2
batteries without any RM, with TEMPO dissolved in the electrolyte,
and with immobilized TEMPO on the cathode were also examined
(current density of 0.1 mA cm
2) (Fig. 5(f)). The increase in the
discharge capacity upon the addition of TEMPO in the Li-O2 battery
can be ascribed to the enhanced charge transfer. With immobilized
Please cite this article in press as: J.-H. Baik, et al., Enhanced cycle stability of rechargeable Li-O2 batteries using immobilized redox mediator on
air cathode, J. Ind. Eng. Chem. (2019), https://doi.org/10.1016/j.jiec.2019.11.015
5
TEMPO on the cathode, the discharge capacity further increases,
clearly indicating the good stability of the immobilized TEMPO.
Conclusions
In summary, a nonaqueous Li-O2 battery with high performance
was fabricated using a TEMPO-immobilized cathode that was
prepared by a simple coating and grafting process. The effect of
immobilized TEMPO on the cathode was verified by comparing the
electrochemical performances of Li-O2 batteries with immobilized
TEMPO on the cathode, TEMPO dissolved in the electrolyte, and in
the absence of TEMPO. The immobilized TEMPO on the cathode
suppressed the degradation of TEMPO at the Li metal anode and
extended the redox mediated Li2O2 oxidation over repeated cycles.
This study introduces a simple and effective strategy to modify the
electrodes of advanced energy storage systems containing RMs.
The insights from these studies will allow the utilization of RMs
more efficiently, using a smaller amount, to prolong their lifespan
and also enhance the battery performance.
Declarations of interest
None.
Acknowledgments
Funding: This work was supported by the National Research
Foundation of Korea (NRF), Korea government (MSIT) (No.
NRF-2018R1A5A1024127), Korea government (MEST) (NRF-
2016R1E1A1A01942936)), and the Supercomputing Center/Korea
Institute of Science and Technology Information with super-
computing resources, which provided technical support
(KSC-2017-C2-0029).
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Please cite this article in press as: J.-H. Baik, et al., Enhanced cycle stability of rechargeable Li-O2 batteries using immobilized redox mediator on
air cathode, J. Ind. Eng. Chem. (2019), https://doi.org/10.1016/j.jiec.2019.11.015