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i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 9 2 8 9 e1 9 2 9 4

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Effect of CO2 partial pressure on the cathode lithiation


in molten carbonate fuel cells

Juyoung Youn a,b, Bohyun Ryu a, Miyoung Shin a, Hyunwoo Kang a,


Heenam Kim a, Ingab Chang a, Taewon Lee a, Hyuksang Kwon b,*
a
Fuel Cell Development Center, Doosan Heavy Industries & Construction Co., Ltd, Republic of Korea
b
Corrosion and Energy Storage Materials Laboratory, Department of Material Science and Engineering, KAIST,
Daejeon 305-811, Republic of Korea

article info abstract

Article history: Nickel cathode is transformed to lithiated nickel oxide by oxidation and lithiation during
Received 2 June 2011 the conditioning process for molten carbonate fuel cells. In the lithiation process, the
Received in revised form amount of lithium inserted into nickel oxide depends on the oxygen and CO2 composition
28 May 2012 and this affects the performance of nickel cathode. In this paper, CO2 interruption tech-
Accepted 1 June 2012 nique was applied to investigate the effects of CO2 interruption on the lithiation of nickel
Available online 5 July 2012 oxide. During the CO2 interruption for 24 h in cathode operating at 20 mA/cm2, the
carbonate ion in electrolyte was decomposed into oxygen and CO2. With the additional
Keywords: oxygen on cathode surface, Ni2þ is oxidized to Ni3þ with formation of cation vacancy in
Molten carbonate fuel cell NiO. The lithium content of cathode increased from 3.0 at.% to 17.4 at.% (over-lithiation)
MCFC and hence LiNiO2 phase was formed in the cathode. Cathode surface area is increased by
Cathode a decrease in NiO particle size with the formation of micropores. The morphological
Lithiation change in cathode enhanced its electrochemical performance in the single cell. Cell voltage
Oxidation of the single cell that has been subjected to CO2 interruption at 120 mA/cm2 was enhanced
CO2 interruption by 300 mV, due primarily to the reduction in the internal resistance from 2.0 to 0.8 U cm2
and also in the charge transfer resistance from 3.0 to 1.1 U cm2.
Copyright ª 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

1. Introduction is oxidized to Ni3þ by oxygen with the formation of cation


vacancy. Lithium ion from the electrolyte inserted into the
Lithiated nickel oxide is commonly used as a cathode in cation vacancy to neutralize the charge in the lithiation step
molten carbonate fuel cells and several reduction mecha- represented by Eq. (2).
nisms such as peroxide mechanism, super oxide mechanism

and poly carbonate mechanism have been proposed [1]. Ni þ CO2
3 /NiO þ CO2 þ 2e : oxidation step (1)
Porous nickel cathode, LixNi1xO, is usually oxidized and
þ 2þ 3þ
lithiated in the pretreatment step (or conditioning step) that Li þ O2 2
electrolyte þ 2NiNi 4LiNi þ 2NiNi þ Osolid
involves the increase in temperature from room temperature : lithiation step (2)
to the operating temperature.
In the pretreatment step, porous nickel cathode reacts with During the cathode oxidation, the open circuit potential of
oxygen or oxygen ion, thereby forming nickel oxide; the cathode increased from 0.9 V to 0.5 V vs. a standard oxygen
cathode oxidation step expressed by Eq. (1). Then, Ni2þ of NiO reference electrode (SOR, Au/33.3% O2/66.7% CO2) and then

* Corresponding author. Tel.: þ82 42 350 3326.


E-mail address: hskwon@kaist.ac.kr (H. Kwon).
0360-3199/$ e see front matter Copyright ª 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ijhydene.2012.06.006
19290 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 9 2 8 9 e1 9 2 9 4

increased further from 0.5 V to 0.1 V vs. SOR during the


cathode lithiation again [2e4,6]. Both the cathode oxidation 3. Results and discussion
and lithiation is very important steps in order to obtain good
electrocatalytic and high electronic conductivity of the 3.1. Change in the cell performance characteristics
cathode. The amount of lithium inserted nickel oxide solid during CO2 interruption
solution (LixNi1xO) is in the range of 0.5e4 at.% that is
determined by the equilibrium reaction of the electrolyte with During the CO2 interruption for the single cell, the cell voltage
oxygen. Belhomme et al. reported that the lithium content in decreased from 1.04 V to about 0.6 V as shown in Fig. 1(a). The
NiO was relatively low in the range of 0.1 and 0.5 at.%, [5]. decrease in the cell voltage was caused by the drop of the
However, it varies depending on the equilibrium reaction cathode potential at a current density of 20 mA/cm2. For the 3
between molten carbonate and oxygen in which O2 and CO2 electrode cell, the cathode potential was decreased from
play an important role in the cathode lithiation [6,7]. Morita et about 0.1 V to about 0.5 V vs. SOR (standard oxygen
al. reported that single cell performance was enhanced after reduction potential) during CO2 interruption as shown in the
CO2 gas shut down for 15 min at a current density of 150 mA/ Fig. 1(b). During the CO2 interruption period, the anode
cm2, which may be associated with the decrease in the potential did not change. After the CO2 interruption, the
internal resistance [8]. However, the effects of various factors values of the cell voltage and cathode potential were recov-
such as CO2 interruption time and operating current density ered to the initial values. According to Ryu et al. [3], oxidation
on the cell performances have not yet been systematically of the nickel cathode proceeded in a potential range of
studied. It appears the change in gas composition caused by 0.9 w 0.5 V vs. SOR and the lithiation of NiO cathode pro-
the CO2 gas shut down may affect the electrochemical char- ceeded from the range of 0.5 V vs. SOR. Based on the refer-
acteristics of the electrode and hence the cell performance. ence result, an additional lithiation (over-lithiation) of
It is research objective of the present work to examine the cathode was expected, because of the decrease in its potential
effects of the CO2 interruption time and current density on the during CO2 interruption.
cell voltage, cathode potential and impedance of single cell.

2. Experimental

The CO2 interruption test was carried out in a 10  10 cm2


sized single cell where porous NiAl alloy anode, porous lithi-
ated nickel oxide cathode and lithium aluminate matrix were
used. The electrolyte was a mixture of 70 mol% Li2CO3e30 mol
% K2CO3. To measure the electrode potential in the single cell,
a standard oxygen reference electrode (SOR, Au/33.3%O2/
66.7%CO2) was connected to the matrix with a salt bridge
(50 wt.% (Li0.7K0.3)2CO3 þ 50 wt.% LiAlO2). The reference gas
flow rate was kept at 10 cc/min. Cathode CO2 gas was inter-
rupted for 15 min at 20 mA/cm2. The electrochemical
measurements were performed in single cell operation mode
at 120 mA/cm2. In order to measure the electrochemical
characteristics of the cell, the cell polarization test, EIS (Elec-
trochemical Impedance Spectroscopy) test and gas chroma-
tography (HP 7890) measurements were performed. EIS was
performed with an excitation voltage of 10 mV in frequency
range of 50 kHze10 mHz with a Solartron 1260, frequency
analyzer and a 1287, electrochemical interface. After per-
forming all the electrochemical measurements, the CO2
interruption was repeated 12 times.
The morphological change in cathode during the CO2 inter-
ruption was examined by scanning electron microscope (SEM;
JEOL, JSM-6390) after the electrolyte in the cathode was extrac-
ted by 5 mol% acetic acid at 50  C for 2 h. X-ray diffraction (XRD;
Rigaku, D/MAX 2500H) test was carried out to characterize the
change in crystal structure of cathode. The size distribution of
pore in cathode was analyzed by Hg-porosimeter (Micrometics,
AutoIV9505). And the surface area of cathode with pores was
measured using BET analyzer (TristarTM II 2030, ASAP 2010). The
lithium content in the CO2 interrupted cathode was measured Fig. 1 e (a) Single cell voltage behavior. (b) Cathode
by inductively coupled plasma-atomic emission spectroscopy potential behavior of 3 electrode cell during CO2
(ICP-OES; Perkinelmer, 5300DV). interruption at 20 mA/cm2.
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 9 2 8 9 e1 9 2 9 4 19291

Fig. 2 represents effects of CO2 interruption time on the


polarization behaviors of single cell. Cell voltage at 120 mA/cm2
was improved stepwise with an increase in CO2 interruption
time. During the initial 30 min, the performance improvement
was not significant, but during 30 mine150 min, the cell voltage
was significantly improved, and thereafter the cell voltage
reached a steady state value to 210 min at 120 mA/cm2.
In order to investigate the mechanism related to the enhanced
cell performance, cell resistance was measured by EIS. As shown
in the Nyquist plot of the cell in Fig. 3, cell resistance decreased
with CO2 interruption time. The real parts of the resistance were
shifted to the left with the CO2 interruption time, and the diam-
eter of the semicircle was also reduced. An equivalent circuit
corresponding to the impedance spectra was proposed by modi-
fying the Randles equivalent circuit as presented in Fig. 4(a) [3,9].
The modified equivalent circuit consists of an internal resistance;
Rir, a charge transfer resistance; Rct, a mass transfer resistance;
Rmt, a inductance; L and a constant phase element replaced
a double layer capacitance; CPE. CPE in the equivalent circuit
replaces a double layer capacitance and indicates the fractal
geometry of surface and the capacitance of oxide layer. The sum
of resistance, Rtotal, is defined as Rtotal ¼ Rir þ Rct þ Rmt. According
to Ganesan et al., the high frequency plot has been correlated with
the charge transfer process while the low frequency plot has been
correlated with a slow process (mass transfer or slow homoge-
neous reaction) [10]. The overall cell resistance decreased with
CO2 interruption time as shown in Fig. 4(b). The internal resis-
tance decreased from 2.0 U cm2 to 0.8 U cm2, and the charge
transfer resistance decreased from 3.0 U cm2 to 1.1 U cm2. The
internal resistance behavior is in a good agreement with the
results of Morita et al. [8]. However, the mass transfer resistance
of single cell in the low frequency of the Nyquist plot slightly
increased. A possible reason would be that the electrolyte is
decomposed and an electrolyte thin film was formed at the
electrode surface during CO2 interruption.

3.2. Structural characterization of cathode after CO2 Fig. 3 e The Nyquist plots from EIS analysis of single cells
interruption during CO2 interruption at 620  C.

The enhancement of cell performance is correlated to the


reduction in both the internal resistance and the charge
transfer resistance. After CO2 interruption, the electrolyte was
extracted from the cathode and the lithium content in the
cathode was analyzed by ICP-OES. The lithium content of the
CO2 interrupted cathode increased from 3.0 at.% to 17.4 at.%
with the interruption time as shown in Fig. 5. This result
suggests that more lithium is inserted into the cathode. Thus,
the cathode can be considered as over-lithiated during the CO2
interruption process. It appears that the equilibrium state of
LixNi1xO was changed by the gas atmosphere during CO2
interruption. According to Houten et al. [11], the electrical
resistance decreases with lithium content or with the increase
in Ni3þ concentration in the cathode. Therefore, the cell sub-
jected to CO2 interruption exhibited higher electrical
conductivity and lower internal resistance than that without
CO2 interruption.
Due to the higher lithium content in the nickel oxide
Fig. 2 e IeV curve behavior of single cells with CO2 lattice, the cathode morphology also changed as shown in
interruption time at 620  C. Fig. 6. The nickel oxide particles of the cathode agglomerate
19292 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 9 2 8 9 e1 9 2 9 4

Fig. 4 e (a) Equivalent circuit for single cell (b) resistance


behavior from EIS analysis of single cells during CO2
interruption.

were split and their size diminished. Moreover, NiO particles


were evolved from sphere shape to angulate shape.
XRD analysis was performed to analyze structural char-
acteristics of the cathode. Whereas the non-treated cathode Fig. 6 e (a) Cathode surface morphology before CO2
(0 h sample) showed only NiO peaks, the CO2 interrupted interruption. (b) After CO2 interruption for 24 h.
cathode (2 h, 8 h samples) had additional lithium nickel oxide
(LiNiO2) peak as shown in Fig. 7. Lin et al. reported that LiNiO2
LiNiO2 is not detected in MCFC condition, because the amount
synthesized from NiO and Li2CO3 was also formed by the
of lithium inserted into NiO is depended on the gas concen-
oxidation of Ni, creation of cation vacancies and lithium
tration and the temperature. In this work, the oxidation of Ni
insertion. The rate-limiting step is the Ni oxidation and the
or Ni2þ by a high oxygen concentration at the cathode surface
vacancies creation [12]. Although the formation mechanism
accelerated the formation of the lithium nickel oxide.
of LiNiO2 is similar to the lithiation mechanism in MCFCs,
The cathode surface area determined by BET analysis
(Fig. 8(a)) dramatically increased from 0.49 m2/g to 2.27 m2/g
with CO2 interruption time. As shown by SEM (Fig. 6), this

Fig. 5 e Lithium content in LixNi1LxOy cathode of single


cells during CO2 interruption. Fig. 7 e XRD patterns of cathode during CO2 interruption.
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 9 2 8 9 e1 9 2 9 4 19293

Fig. 8 e (a) Cathode surface area. (b) Cathode pore size Fig. 9 e (a) Net produced oxygen in cathode exhaust with
distribution during CO2 interruption. CO2 interruption time and electrolyte decomposition (b)
electrolyte filling content in LiNiO cathode after single cell
evolution is related to the decrease in NiO particle size and the operation.
splitting of nickel oxide. Furthermore, after CO2 interruption
for 24 h, the pore size of NiO particle in the cathode agglom-
erate was diminished and micropores were developed with
resistance of single cell decreased with CO2 interruptions as
the time, as can be seen in the Fig. 8(b). The large surface area,
shown in the Fig. 4(b).
small particle size and fine pores in NiO cathode may improve
the electrochemical reaction activity, and the charge transfer
3.3. Electrolyte decomposition and CO2 interruption
mechanism

Table 1 e Mechanism of lithiaiton during CO2 The additional lithium source inserted in NiO was proceeded
interruption. from Li2CO3 in the electrolyte that is partially decomposed by
Step Reaction the CO2 interruption. When the cathode CO2 gas is insufficient
at 20 mA/cm2, Li2CO3 would be decomposed to produce O2 (3)
1 Depletion of CO2 1=2O2 þ ð Þ þ 2e 4CO2
3
or oxide ion (4) and CO2. In the equation (3), the decomposition
in cathode reaction
 of carbonate is irreversible reaction because of the continuous
2 Production of CO2 CO2
3 41=2O2 þ CO2 þ 2e [12] consumption of CO2 by the cathode reaction. In the case that
gas by carbonate CO2
3 4CO 2 þ O 2

decomposition the electrolyte is not decomposed and CO2 gas was not
3 Vacancy creation 1=2O2 þ 2Ni2þ  2
lattice þ 2e 4Olattice
produced, the single cell voltage decreases to zero voltage or
and formation of minus voltage by insufficient reactant gas.
þV00Ni;lattice þ 2Ni3þ
Ni3þ by the effect of
additional O2 on [13]
cathode surface 1 
4 Additional lithium V00Ni;lattice þ Liþ 42Li0Ni;lattice þ 2h0 [13]
CO2
3 / O2 þ CO2 þ 2e (3)
2
insertion into vacancy
(Over-lithiation)
CO2
3 /O
2
þ CO2 (4)
19294 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 9 2 8 9 e1 9 2 9 4

Fig. 9(a) shows a result of the cathode exhaust gas analysis, Planning (KETEP) grant funded by the Korea Government
net produced oxygen gas by the electrolyte decomposition Ministry of Knowledge Economy. (No. 2008-N-FC12-J-04-1000).
increased during CO2 interruption and net produced CO2 by the
electrolyte decomposition was surely consumed. Moreover, as
an evidence of electrolyte decomposition, we confirmed that references
the electrolyte content in the cathode pores also decreased
with CO2 interruption time as shown in Fig. 9(b).
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This work was supported by the New & Renewable Energy of cobalt in contact with molten carbonate. Solid State Ionics
the Korea Institute of Energy Technology Evaluation and 1999;124:149e60.

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