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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.
2. Experimental
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.
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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4. Conclusion
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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.