Solid State Ionics 192 (2011) 398–403

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Solid State Ionics

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s s i

Co-electrolysis of CO2 and H2O in solid oxide cells: Performance and durability
Christopher Graves a,b,⁎, Sune D. Ebbesen a, Mogens Mogensen a
a
Fuel Cells and Solid State Chemistry Division, Risø National Laboratory for Sustainable Energy, DTU, 4000 Roskilde, Denmark
b
Lenfest Center for Sustainable Energy, and Department of Earth and Environmental Engineering, Columbia University, 500 West 120th St, New York, NY 10027, USA

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

Article history: This study examines the initial performance and durability of a solid oxide cell applied for co-electrolysis of
Received 1 September 2009 CO2 and H2O. Such a cell, when powered by renewable/nuclear energy, could be used to recycle CO2 into
Received in revised form 28 May 2010 sustainable hydrocarbon fuels. Polarization curves and electrochemical impedance spectroscopy were
Accepted 11 June 2010
employed to characterize the initial performance and to break down the cell resistance into the resistance for
Available online 16 July 2010
the specific processes occurring during operation. Transformation of the impedance data to the distribution
Keywords:
of relaxation times (DRT) and comparison of measurements taken under systematically varied test
Solid oxide electrolysis cell conditions enabled clear visual identification of five electrode processes that contribute to the cell resistance.
Co-electrolysis The processes could be assigned to each electrode and to gas concentration effects by examining their
Synthesis gas dependence on gas composition changes and temperature.
Synthetic fuels This study also introduces the use of the DRT to study cell degradation without relying on a model. The
Impedance spectroscopy durability was tested at consecutively higher current densities (and corresponding overpotentials). By
Distribution of relaxation times analyzing the impedance spectra before and after each segment, it was found that at low current density
High temperature electrolysis
operation (− 0.25 A/cm2 segment) degradation at the Ni/YSZ electrode was dominant, whereas at higher
current densities (− 0.5 A/cm2 and − 1.0 A/cm2), the Ni/YSZ electrode continued to degrade but the serial
resistance and degradation at the LSM/YSZ electrode began to also play a major role in the total loss in cell
performance. This suggests different degradation mechanisms for high and low current density operation.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction was initially investigated in the 1960s as a means to produce O2 for life
support and propulsion in submarines and spacecraft [10–15].
Fossil fuels and biomass are the most common feedstocks for Research on using solid oxide cells for this purpose continues today
production of hydrocarbon fuels. However, using renewable or [16–22]. Recently, there has been a surge of research activity for
nuclear energy, CO2 and H2O can be recycled into sustainable electrolysis of H2O [24–32,43,44], CO2 [26,31,33–35] and CO2/H2O
hydrocarbon fuels in a non-biological process. Renewable/nuclear mixtures [36–42] for fuel production purposes, using state-of-the-art
energy sources, as heat, electricity, or light, can drive the splitting of cells.
CO2 and H2O to reverse the process of combustion [1]. A process to The cell operation is illustrated in Fig. 1. When both H2O and CO2
produce such fuels has three stages: (1) CO2 capture, (2) storage of are supplied to the Ni/YSZ electrode for co-electrolysis, the water–gas
the renewable/nuclear energy as chemical energy by dissociation of shift (WGS) equilibrium may play a role in the CO or H2 production
CO2 and/or H2O, and (3) fuel synthesis using the dissociation (YSZ = yttria-stabilized zirconia). Since the cell resistance for CO2
products. For a fully closed-loop fuel cycle analogous to the hydrogen electrolysis is slightly higher than that for H 2 O electrolysis
fuel cycle, the CO2 must be captured from the atmosphere, which is [26,31,34,35,39–42] and at the cell operating temperature of 850 °C
technically feasible [2–9]. A promising means of efficient dissociation the WGS equilibrium favors the reverse reaction, it is expected that
is by high temperature electrolysis of CO2 and/or H2O in solid oxide part of (possibly most of [40]) the CO produced results from reverse
cells (SOCs) [1,10–44] to yield synthesis gas (an energy-rich gas WGS. Co-electrolysis may be advantageous for process simplicity,
mixture of CO and H2). Finally, liquid fuel synthesis from syngas, e.g. eliminating the need for a separate reverse WGS reactor to prepare
Fischer–Tropsch synthesis [45], is a well-known technology. syngas with the H2/CO ratio needed for catalytic fuel synthesis.
This paper describes experimental results for co-electrolysis of CO2 Recently, long-term (N200-hour) durability studies have been
and H2O in a solid oxide cell. Electrolysis of CO2 and CO2/H2O mixtures reported for H2O [23,24,28,32,39,44,46,47] and CO2 [35] electrolysis,
and in a companion paper [42] we report the durability for co-
⁎ Corresponding author. 500 West 120th St., 918 S.W.Mudd, MC 4711, New York,
electrolysis at low current density. In general, according to literature,
NY 10027, USA. Tel.: + 1 212 854 2905; fax: + 1 212 854 7081. degradation at the Ni/YSZ electrode seems to dominate during
E-mail address: [email protected] (C. Graves). electrolysis and apparently involves accumulation of impurities at

0167-2738/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.ssi.2010.06.014
 C. Graves et al. / Solid State Ionics 192 (2011) 398–403 399

employed [55], including analysis of differences in impedance spectra

(ADIS) [56] and transformation of the impedance data to the
distribution of relaxation times (DRT) [57–59]. Both methods increase
the resolution of the peaks of the specific processes at their
characteristic frequencies, which is helpful for identifying the
different processes. In the present study the DRT method is used to
analyze the cell performance and degradation.
In the present work we examined the co-electrolysis performance
of a solid oxide cell and studied the durability during co-electrolysis at
consecutively higher current densities. Analysis of the DRT of the
impedance spectra measured at various conditions before and after
long-term testing segments is also introduced as a way to study the
cell degradation mechanisms. In this study, the DRT technique enables
identification of the rate-limiting processes that contribute to the cell
impedance, their relative resistances, and how they change over time,
without relying on a model (equivalent circuit or otherwise) and the
assumptions inherent in a model. The processes that are responsible
for changes in cell performance can therefore be identified
unambiguously.

Fig. 1. Diagram of co-electrolysis of CO2 and H2O in a solid oxide cell, as part of a 2. Experimental
renewable fuel cycle. The electrode reactions are also given.
A planar Ni/YSZ-supported solid oxide cell produced at Risø DTU
was tested as an electrolysis cell. The cell consisted of a dense thin YSZ
electrolyte sandwiched between a porous Ni/YSZ composite negative-
the three-phase boundary (TPB) between the gas, Ni particles and YSZ electrode and a porous LSM/YSZ (LSM = lanthanum strontium
particles where the reactions occur [28,32,35,42,48,49]. Several manganite) composite positive-electrode. The cell type and dimen-
mechanisms for degradation have been proposed, and the mechanism sions and the test set-up have been described elsewhere [42]. In the
might depend heavily on the gas atmosphere—impurities may present study a Ni wire was used for sealing at the side of the Ni/YSZ
originate from the test set-up [28,32], from the cell materials [48], electrode. Initially DC polarization (i–V) curves and AC impedance
and/or from the gasses [35,42,49], or the gas atmosphere in spectra (IS) were measured at 850, 750 and 800 °C with various gas
combination with high temperature (e.g. 90% steam at 950 °C) may atmospheres of H2/H2O/CO/CO2 mixtures supplied to the Ni/YSZ
induce mobility of Ni leading to degradation of the electrode cathode (always at a total flow rate of 25 L/h) and oxygen or air
microstructure [32]. Characterizing cell durability is complicated by supplied to the LSM/YSZ anode (50 L/h). The impedance spectra were
the fact that cell performance sometimes temporarily degrades measured using an external shunt and a Solartron 1255B frequency
(passivates) and then recovers (activates), and the real long-term response analyzer, without DC bias with an AC amplitude of 60 mA in
degradation is occurring simultaneously [32,42]. The magnitude of the the frequency range of 82,451 to 0.082 Hz with 6 or 15 points per
cell operating voltage or resulting current density may also affect the frequency decade (15 for use in the DRT transform). The impedance
durability. Cell durability at high current density (N0.5 A/cm2 data were corrected using the short-circuit impedance response of the
electrolysis) has not been widely reported, although high current test set-up.
density operation may be necessary for an economical synthetic fuel During fuel cell and electrolysis cell polarizations, the cell
production process [1]. temperature varied since only the oven temperature was kept
By analyzing the impedance spectra measured at systematically constant. During fuel cell polarizations, the ohmic heating of the cell
varied test conditions, the cell resistance can be broken down into raised the temperature measured at the thermocouple positioned at
contributions from the electrodes and electrolyte. Ideally, a three- the center of the cell by up to 6 °C relative to the temperature
electrode set-up could be used. However, using a reference electrode measured at OCV. During electrolysis polarizations, the cell consumed
with thin-electrolyte technological solid oxide cells is not possible— heat and lowered the measured temperature by up to 1 °C and then at
proper placement of a reference electrode is difficult and measure- higher cell voltage approaching the thermoneutral voltage the
ments are known to be distorted due to non-uniform current temperature slightly increased to up to 1 °C higher than that
distribution [50–52]. Consequently, breaking down the resistance measured at OCV. The temperature measured by a thermocouple
involves deconvolution of impedance spectra that have overlapping positioned at the corner of the cell was within 1 °C of that measured at
processes (similar characteristic frequencies). Prior methods of the center of the cell, at OCV. During fuel cell polarizations, the corner
breaking down the cell resistance relied on performing a complex temperature reached 3 °C lower than the center temperature, and
nonlinear least-squares regression to an equivalent circuit composed during electrolysis polarizations the difference of the two tempera-
of an array of serially connected circuit elements (Voigt measurement ture measurements remained below 1 °C.
model)—an inductor (L), a resistor (R), and five serial RQ (resistor in After the initial characterization, the cell was operated in
parallel with a constant phase element) subcircuits, or in common galvanostatic mode, with a mixture of 45% CO2, 45% H2O, and 10%
equivalent circuit notation, LR(RQ)(RQ)(RQ)(RQ)(RQ) [53,54]. This H2 with total flow rate of 25 L/h supplied to the Ni/YSZ cathode and
equivalent circuit has 17 parameters (one for each L element, one for 100% O2 supplied at 50 L/h to the LSM/YSZ anode, at current densities
each R element, and two per Q element) that must be fitted to the of − 0.25, − 0.5, and −1 A/cm2, operating for 382, 206, and 212 h
impedance data, which requires careful and difficult analysis respectively at each galvanostatic segment. The cell voltage history
involving fixing some parameters while fitting others. Alternative during operation at − 0.25 A/cm2 was previously shown in a
methods of breaking down the resistance or at least for providing companion paper [42]. The same set of electrochemistry measure-
input data and constraints to the equivalent circuit would be useful. ments as before the galvanostatic test was conducted after each
Recently, alternative methods to identify processes have been segment, at the same temperatures and gas compositions.
400 C. Graves et al. / Solid State Ionics 192 (2011) 398–403

3. Results and discussion (45% CO2 + 45% H2O + 10% H2), reactant utilization will bring the
reactant/product ratio closer to 1, reducing Rconv and Rdiff—hence the
3.1. Performance relative lack of curvature in that i–V curve. Further study of these
effects is important if high reactant utilization is necessary.
Fig. 2 shows i–V curves for oxidation and reduction in H2/H2O/CO/ The IS measurements at OCV for the same gas compositions (Fig. 3)
CO2 mixtures at 850 °C. The gas mixtures used were 50% H2O + 50% agree with the i–V curves—the resistance for reduction and oxidation
H2, 50% CO2 + 50% CO, and 25% H2O + 25% CO2 + 25% H2 + 25% CO, of the co-electrolysis gas composition is higher than for H2O/H2 and
and 45% H2O + 45% CO2 + 10% H2. The first three all give 50% reactants lower than for CO2/CO, and closer to that of H2O/H2. It can be seen that
for either fuel cell or electrolysis operation, and the last is the the serial resistance, RS, which is almost entirely the ohmic resistance
composition that was subsequently used for the electrolysis durability of the electrolyte, contributes 40–50% of the total resistance at OCV at
test. Because the free energies of the CO2 and H2O dissociation (to this temperature. From the Nyquist plot, it is not clear how much each
yield CO and H2 respectively) reactions are nearly equivalent at this electrode contributes to the polarization resistance, RP, and what
temperature [60], the open-circuit voltage (OCV) for the three 50%- electrode processes might be contributing. The impedance data,
reactants compositions are nearly all equivalent, as can be seen in the measured at systematically varied temperature and gas compositions
figure. at each electrode, were transformed to the DRT and compared to
The cell exhibited a high performance for co-electrolysis of CO2/ resolve these processes.
H2O mixtures, comparable to the performance for steam electrolysis Fig. 4 shows the DRT for three different gas atmospheres at 850 °C.
which is known to be high [61]. As has been reported for similar cells Transforming to the DRT enhances the frequency-domain resolution
[26,31,34,35,39–42], the cell exhibited slightly higher performance for of the impedance response. By varying the gas composition supplied
H2 oxidation and H2O reduction than for CO and CO2 respectively. For to the Ni/YSZ electrode, only the Ni/YSZ electrode impedance
the 25%-each composition, co-electrolysis performance was between processes should be affected, and the same goes for the LSM/YSZ
that of CO2 and H2O electrolysis and closer to H2O. This suggests that electrode. Five rate-limiting processes are visible in the DRT plot—2
besides the CO2 and H2O electrolysis reactions, the reverse WGS LSM/YSZ electrode processes, 1 Ni/YSZ process, and 2 low-frequency
reaction occurs. The role of the reverse WGS is further studied, using processes mainly at the Ni/YSZ side of the cell, which were
different gas composition variations, in ref. [42]. The degree to which independent of temperature (not shown) and correspond to gas
reverse WGS is responsible for CO production cannot be determined conversion and gas diffusion impedance [63–65]. The electrode
from these results. True quantification of the relative amounts of the process with the highest characteristic frequency, which is indepen-
reactions taking place would require 18O isotope tracing or a similar dent of any gas changes, is ascribed to the LSM/YSZ electrode based on
method. However, whether part of the syngas is produced by the WGS the similarities of the summit frequency and gas-independence as
equilibrium has little effect on the energy demand of syngas found using simplified cells composed of only LSM/YSZ (symmetrical
production in the cell, because the cell's internal resistance can cells) in another study [53,54]. The summit frequencies are in
supply the heat needed for either the electrochemical or catalytic approximate agreement with the five cell processes found by the
reactions. equivalent circuit method for this type of cell (described earlier). The
From Fig. 2 it is also observed that at higher current densities the DRT therefore enables identification of the rate-limiting processes
resistance increases for the three 50%-reactants i–V curves. It appears that contribute to the total impedance of a cell without relying on a
that a limiting current density is approached. This effect is often model. Modeling would of course still be very useful to study the
explained as a gas diffusion limitation of the reactants inside the nature of the processes. The breakdown of the total cell impedance
electrodes [41,62]. However, it is possible that the increased into these processes could at this point be quantified by modeling the
resistance may arise from effects related to the test set-up instead DRT (e.g. applying a measurement model by fitting distribution
of the gas transport in the electrode microstructure—gas conversion functions to the transformed data to quantify the peaks, or deriving
resistance [63,64], Rconv, and/or gas diffusion resistance due to a and applying an electrochemical model). However for this study the
volume of stagnant gas outside the porous electrode structure [64,65], DRT is used as is, to study the degradation mechanism of the cell by
Rdiff. Rconv and Rdiff are both minimal when the reactant/product ratio simply identifying which processes are affected by long-term testing.
is 1. Therefore, when the gasses are supplied at a reactant/product
ratio of 1 (the 50%-reactants tests), Rconv and Rdiff are smallest at OCV, 3.2. Durability
and reactant utilization resulting from polarization will reduce this
ratio and thereby increase these types of resistance. On the other During the galvanostatic segments, the cell voltage increased at a
hand, when the gasses are supplied at a reactant/product ratio of 9 faster rate at higher current densities (or correspondingly, higher cell
voltages) (Fig. 5). During the low current density (− 0.25 A/cm2)

Fig. 2. DC polarization (i–V) curves for oxidation and reduction of chosen mixtures of Fig. 3. Nyquist plot of impedance spectra measured at OCV for the three 50%-reactant
H2, H2O, CO, and CO2. gas compositions as in Fig. 2.
 C. Graves et al. / Solid State Ionics 192 (2011) 398–403 401

Fig. 6. Nyquist plot of impedance spectra measured at OCV before and after each
Fig. 4. Distribution of relaxation times (DRT) for three impedance measurements galvanostatic test segment.
measured at OCV with various gas compositions supplied to the anode and cathode.

the Ni/YSZ electrode process has grown, whereas the lower-frequency

segment, the cell voltage increased initially during the first 100 h and LSM/YSZ (LSMLF) peak has not been affected. At first glance the high-
then leveled off to a slow degradation rate of 0.005–0.008 mV/h during frequency LSM/YSZ (LSMHF) peak appears to have grown slightly—
the last 100 h. The minor passivation and activation of the cell during the however since the DRT result is the sum of all the peaks, the growth of
first 200 h was much less pronounced compared with what has been the nearby Ni/YSZ peak can visually boost the sum near the LSMHF
observed for other H2O [28,32,47], CO2 [35], and co-electrolysis tests peak (the inset of Fig. 7 illustrates this with example Gaussian peaks
[42]. If the previously observed passivation/activation is rooted in that might fit the DRT data). After the −0.5 A/cm2 segment and
impurities, this test illustrates the inconsistency of impurity-related especially after the −1 A/cm2 segment, however, it is clear that the
passivation phenomena since the same gasses, same cell type and nearly LSM/YSZ electrode has degraded as well; an enlarged Ni/YSZ peak
identical test set-up were used in this test as in some of the others cannot account for the large increases near LSMLF and LSMHF even if
(excluding the tests that used glass sealing, which was believed to the enlarged Ni/YSZ peak is represented by a Gaussian (or any type of)
contribute to degradation by supplying silica impurities). During the distribution with the maximum width that can fit under the DRT sum.
higher current density segments, it is clear that the degradation rate is This analysis suggests different degradation mechanisms for high
significantly faster, on the order of 0.1 mV/h, although the degradation and low current density operation. At low current density, degrada-
rate was not allowed to fully level off. tion at the Ni/YSZ electrode dominates, as has been reported for
The impedance spectra measured before and after each segment various electrolysis durability tests (discussed earlier), whereas at
(Fig. 6) show an increasing serial resistance (RS), especially after the higher current densities, both serial resistance and LSM/YSZ electrode
final segment at −1 A/cm2. The high-frequency contributions to the degradation play a significant role. The Ni/YSZ electrode degradation
impedance also appear to have enlarged with the consecutively seems to be related to impurities that accumulate at the TPB, as
higher current densities. As expected, the low-frequency gas discussed earlier [28,32,35,42,48,49]. Removing these impurities may
concentration impedance arcs do not appear to have noticeably result in durability with only limited degradation when operated at
changed. However, not much more can be learned from the Nyquist low current densities [49]. Although Ni is a good catalyst for coking
plot (Fig. 6). The DRT can be used to reveal more information about reactions, carbon deposition is not thermodynamically favored at any
which processes were affected during each segment of long-term of the conditions that the cell was tested in. Furthermore, a prior study
operation. The DRT does not show RS (nor changes in RS). The DRT and of pure CO2 electrolysis, which would provide more favorable
the Nyquist plots are therefore complementary for analyzing conditions for carbon formation, determined that carbon formation
impedance data. The DRTs of impedance spectra measured before is not a source of degradation [35].
and after the segments (Fig. 7) clearly show that the impedance Since higher current operation induces higher potentials across
contributions related to gas concentration have negligibly changed. each electrode, the different degradation mechanisms might be
The DRTs show that after the −0.25 A/cm2 segment, the resistance of related to the distribution of the potentials and the magnitude of

Fig. 7. DRT of impedance spectra measured at OCV before and after each galvanostatic
Fig. 5. The cell voltage and the rate of change of the cell voltage (insets) measured test segment. Inset: illustration of example Gaussian peaks fitted to the high-frequency
during the 3 consecutive galvanostatic co-electrolysis segments run on the cell. range for “initial” and “after − 0.25 A/cm2” measurements.
402 C. Graves et al. / Solid State Ionics 192 (2011) 398–403

slightly lower than for H2O electrolysis, suggesting that the reverse
WGS plays a role during co-electrolysis. Transformation of the
impedance data to the distribution of relaxation times (DRT) and
comparison of measurements taken under systematically varied test
conditions enabled clear visual identification of five electrode
processes that contribute to the cell resistance. The processes were
assigned to each electrode and to gas concentration effects by
examining their dependence on gas composition changes and
temperature.
The cell durability for co-electrolysis was examined at consecu-
tively higher current densities and corresponding cell voltage. By
analyzing the DRTs of the impedance data measured before and after
each segment of operation, it was found that at low current density
operation (− 0.25 A/cm2) degradation at the Ni/YSZ electrode
dominated, whereas at higher current densities (−0.5 A/cm2 and
−1.0 A/cm2), the Ni/YSZ electrode continued to degrade but the serial
resistance and degradation at the LSM electrode began to play a major
role in the total loss in performance. Considering the economics of
producing synthetic fuels by CO2 recycling, the durability at high
current density operation needs to be improved if the electrolyzer will
be powered by intermittent renewable electricity sources. With a
more constant power supply, however, low current density operation
may be economical and the observed durability at low current density
may be sufficient for synthetic fuel production.

Fig. 8. Scanning electron micrographs of an identical cell that was long-term tested
under high current density electrolysis similar to the test reported in the present study. Acknowledgements
(a) The LSM/YSZ electrode active layer and the entire electrolyte. (b) Closer view of the
electrolyte damage near the interface with the LSM/YSZ electrode. The authors wish to thank J. H. Jørgensen for development of
software for carrying out DRT analysis, and T. Ramos, N. Bonanos, H.
Henriksen, and other colleagues for discussions and technical assistance.
the potential across each component of the cell (the electrodes and
Financial support from the American Chemical Society Petroleum
electrolyte). When this type of cell has been tested as a fuel cell under
Research Fund, and the Programme Commission on Sustainable Energy
similar conditions, far less degradation at high current density has
and Environment, The Danish Council for Strategic Research, via the
been observed [66], suggesting that the degradation observed here
SERC project (www.serc.dk), is gratefully acknowledged.
may be specific to electrolysis operation. One possibility is a build-up
of oxygen partial pressure in and around the electrolyte due to the
potentials applied across the components of the cell [67]. This References
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