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Annu. Rev. Mater. Res. 2003. 33:321–31

doi: 10.1146/annurev.matsci.33.022802.092713
Copyright °
c 2003 by Annual Reviews. All rights reserved

Mogens Mogensen and Kent Kammer
Materials Research Department, Risø National Laboratory, DK-4000 Roskilde, Denmark;
email: mogens.mogensen@risoe.dk; kent.kammer.hansen@risoe.dk

Key Words electrochemical oxidation, oxide anodes, cracking

■ Abstract Recently, a number of papers about direct oxidation of methane and
hydrocarbon in solid oxide fuel cells (SOFC) at relatively low temperatures (about
700◦ C) have been published. Even though the conversion of almost dry CH4 at 1000◦ C
on ceramic anodes was demonstrated more than 10 years ago, the reports about high-
current densities for methane oxidation at such low temperatures are indeed surprising.
Several papers indicate that a catalytic effect (due to the mixed ionic and electronic
conductivity) of CeO2-x is partially responsible for this effect. However, this seems to
contradict previous reports, and thus this issue deserves further analysis.


The requirement of pure hydrogen or hydrogen-rich fuels is a major obstacle for

commercial application of fuel cells in general. The solid oxide fuel cell (SOFC),
which is a high-temperature fuel cell with operation temperatures usually above
600◦ C, has an advantage of being tolerant to nonhydrogen fuels, e.g., CO is a SOFC
fuel, in contrast to low-temperature fuel cells that are poisoned even by rather low
levels of CO. Furthermore, the SOFC operating temperature is high enough to
sustain the process of reforming hydrocarbons, which is the fuel of preference
for most applications. This is generally regarded as another advantage of SOFC.
However, steam reforming poses several problems in practice, as discussed briefly
below. Therefore, several groups of researchers (see e.g., 1–12) have been working
on the possibility of directly feeding the SOFC with hydrocarbons without any pre-
treatment of the fuel. Such direct conversion of methane and higher hydrocarbons
is certainly a challenge. Methane is a fairly stable molecule that needs specific
catalysts in order to react sufficiently fast even at the relative high temperatures
of the SOFC, and both methane and the higher hydrocarbons have the problem of
carbon precipitation (formation of solid carbon compounds) due to cracking. The
higher hydrocarbons in particular are already prone to cracking at relatively low
temperatures of about 500–600◦ C (13). The literature about the direct conversion
of relatively dry hydrocarbons in SOFC is divergent, and several papers in peer
0084-6600/03/0801-0321$14.00 321
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review journals seem to be in direct conflict with many other papers and, to some
extent, with generally accepted knowledge from the catalysis literature. We discuss
this conflict, but before this literature is reviewed, some background information on
steam reforming, hydrocarbon cracking, and carbon deposition in connection with
SOFC is given. A minimum of this kind of knowledge is crucial for the discussion of
the reports about the direct conversion of hydrocarbons in SOFC. Readers desiring
a detailed description of SOFC, steam reforming, and hydrocarbon cracking are
referred to review articles on these subjects (13–16).


The classical materials used by most developers of SOFC are the Ni-YSZ-cermets
as the fuel electrode (YSZ = yttria-stabilized zirconia), YSZ as the electrolyte,
and LSM-YSZ composite as the air electrode (LSM = lanthanum strontium man-
ganate). The excellent electrochemical performance of Ni-YSZ-cermet electrodes
is the reason for this choice.
It is generally agreed that direct feeding of dry hydrocarbons into the fuel cell
must be avoided when using a Ni-containing anode because Ni is an efficient
catalyst for hydrocarbon cracking, and such cracking of hydrocarbon will destroy
the Ni-YSZ anode (10, 16). The carbon whiskers will separate the fine Ni-particle
from the YSZ.
The reformation of hydrocarbons is a well-established technology that most
SOFC developers are using in order to avoid the problems of cracking. The re-
forming of hydrocarbons may, in the SOFC context, take place either as external
reforming (in a separate unit) or as internal reforming inside the hot volume of the
SOFC stack. The simplest is the direct internal reforming on the Ni-YSZ-cermet
anode. Steam reforming seems to be most widely used. The reactions taking place
in steam reforming are

Cn Hm + nH2 O ←
→ nCO + (n + m)/2H2 ,
followed by the shift reaction,

CO + H2 O ←
→ CO2 + H2 .
On the SOFC anode, these reactions are followed by electrochemical oxidation

CO + O2− ← −
→ CO2 + 2e ,
H2 + O2− ← −
→ H2 O + 2e .
There are disadvantages to using internal reforming compared with using an
ideal anode (fuel electrode), which can tolerate dry hydrocarbons. The disadvan-
tages are these:
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(a) Steam reforming requires considerable amounts of water in the fuel [usually
a steam to carbon ratio (S:C) of about two], which results in a diluted fuel.
This has a negative effect on the electromotive force (EMF) of the cell and
thereby the electrochemical efficiency is reduced.
(b) Steam reforming is an extremely endothermic process. In the case of ex-
ternal reforming, this requires a considerable transport of entropy, which
involves an energy loss. Internal steam reforming directly on the anode may
cause large thermal gradients that can damage the cell.
(c) Extra costs are involved in heat exchangers and additional equipment for
steam raising or recycling of the anode exhaust gas.


Explanation of Concepts
Over the past few years, many SOFC researchers have been working on producing
SOFC anodes that can tolerate dry hydrocarbons as fuel. However, the terminology
used in several of the reports has not been clear; therefore, we define our under-
standing of these concepts as follows. Direct conversion of a hydrocarbon means
conversion in the SOFC without pre-mixing the fuel gas with steam or CO2, and
without processing the fuel before it enters the cell stack.
Thus direct conversion is either direct electrochemical oxidation or electro-
chemical oxidation of cracking products. Furthermore, direct electrochemical ox-
idation of a hydrocarbon means a 100% Faradaic-coupled reaction or, in other
words, a hydrocarbon molecule is oxidized electrochemically only if all important
(fast) reaction steps are electrochemical steps.
A direct electrochemical oxidation scheme may theoretically be written as

Cx Hy + (2x + y/2)O2– ← −
→ xCO2 + y/2H2 O + (4x + y)e . 1.

However, Reaction 1 is highly unlikely to occur in one step even in case of the
simplest hydrocarbon, CH4. It might instead proceed as written below (in the case
of methane):

CH4 + O2– ← −
→ CH3 OH + 2e ; 2.
CH3 OH + 2O2– ← −
→ HCOOH + H2 O + 4e ; 3.
HCOOH + O2– ← −
→ CO2 + H2 O + 2e . 4.

Cracking followed by electrochemical oxidation of the cracking products fol-

lows a path as given by
Cx Hy ←
→ xC + y/2H2 ; 5.
2– ← −
C + 2O → CO2 + 4e ; 6.
H2 + O2– ← → 2 H O + 2e −
. 7.
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This is a greatly simplified reaction scheme because the cracking process is

usually highly complex and will often result in many types of products (see below).
It has been argued that the precise mechanism of the hydrocarbon conversion
process is not important for practical applications. As long as the chemical energy
of the hydrocarbon is transformed into electrical energy, the reaction pathway does
not matter. We disagree with this. It is important to distinguish between the two
reaction pathways because the demands on the anode material differ significantly
for these pathways. Whereas an electrode used for direct chemical oxidation need
not be inert to reactions with carbon (as no carbon is formed), oxidation of cracking
products requires that the electrode material must be inactive with respect to reac-
tions with carbon. In order to be effective, an electrode for direct electrochemical
oxidation of hydrocarbon must have a very high turnover rate of the hydrocarbon
bond breaking. Cracking followed by electrochemical conversion of the cracking
products requires an electrode that is both highly active for the cracking of methane
and active for the oxidation of the cracking products. Thus the demands on the
properties of the electrodes are fundamentally different. Also, in a situation where
cracking of the hydrocarbons occurs, it is possible that carbon may block the tub-
ing of the SOFC system. In other words, it is important to know the pathway by
which the conversion of hydrocarbon is to proceed in order to determine which
properties of the anode should be optimized.
Both processes can in principle occur in parallel. It is also noteworthy that
the oxidation might not be complete but proceed only partially. An advantage of
this can be the simultaneous production of electricity, heat, and a useful chemical
compound, i.e., syngas production by partial oxidation of hydrocarbons as (in the
case of methane)
CH4 + O2– ← → CO + H2 + 2e .


Indeed, this concept has been pursued with the main product being the chemical
compound. In such cases, the device is usually not referred to as a SOFC; instead
it is called a ceramic electrochemical reactor [see e.g., (1, 17)] or a dense oxygen
separation membrane [see e.g., (18)].

Carbon Deposition
In order to appreciate the published results about direct conversion of hydrocarbons
in SOFCs, it is necessary to have a brief discussion of our general knowledge about
carbon deposition by pyrolysis of the hydrocarbon. The text below is based on work
of Albright et al. (13) and Rostrup-Nielsen et al. (16). Possible pathways to the
formation of carbon could be

Cx Hy ←
→ xC + y/2H2 , 9.

or by disproportionation of carbon monoxide

CO ←
→ C + CO2 10.

from incomplete oxidation of the hydrocarbon. Carbon can be formed both in the
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Lighter hydrocarbons
Initial hydrocarbon + Gases
Heavier hydrocarbons

Cyclized hydrocarbons


High-molecular-weight hydrocarbons Condensation

Soot Tars

Surface carbon
Figure 1 Diagram of the formation of carbon by pyrolysis of hydrocarbons
through free-radical reactions [after Albright et al. (13) with modification].

gas phase (gas-phase carbon) and on solid surfaces (surface carbon or catalytic
carbon). In general, the carbons consist of high-boiling-point polycyclic aromatics.
The formation of carbon is often a minor reaction of the overall pyrolysis reaction,
but in the SOFC context, it is a problematic reaction because carbon may build
up in the system. The reactions leading to the formation of carbon are complex.
Figure 1 illustrates some possible pathways.
In the present discussion, cokes formed on catalytic surfaces are most inter-
esting. Many types of coke can be formed, depending on the material (surface)
used for the (catalytic) cracking of the hydrocarbon. At least three major families
of coke exist: filamentous, amorphous, and graphitic. Filamentous coke can be
divided into different subtypes depending on the structure of the coke; for exam-
ple, filaments with a rope-like appearance have been found. Normally, filamentous
coke contains metal particles. In contrast to this, amorphous coke contains few or
no metal particles. Graphitic coke is formed mainly at high temperatures (above
900◦ C) and has a higher density than that of other types of coke. The results of
the two pathways may be illustrated by the difference in carbon growth on Ni and
Pt-Fe catalysts. Nickel is good catalyst for cracking of both methane and higher
hydrocarbons. It catalyzes the formation of carbon nanotubes. The nanotube grows
with the nickel particle at its tip. A nickel catalyst is therefore normally not stable
in methane. Another mechanism for growing coke is observed for an alloy of the
Pt-Fe where the tube of coke is extruded from the catalyst particle, which stays in
contact with the support during the growth of the coke.
The stability of the nickel catalyst can be changed by so-called stabilization,
for example, formation of sufficiently small Ni particles. For example, this can be
done by forming a solid solution of nickel with magnesia (Ni1-xMgxO). When the
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oxide is reduced, nickel with a small grain size may be formed, and the growth of
the Ni particles is hindered by the MgO, which cannot be reduced under practical
SOFC anode conditions. If the size of the Ni particles is below about 5 nm, the
formation of filamentous carbon is strongly retarded.
Another possibility is alloying of nickel with copper. It is well known that
copper suppresses the formation of carbon because copper is of limited use as a
catalyst for the C–C bond formation, which in turn suppresses the formation of
carbon. It should also be noted that the effect of nickel stabilization often seems to
be a prolongation of the normally observed incubation time, which elapses before
carbon deposition starts.
Other strategies are to avoid nickel (or other cracking catalysts) by using anode
materials that are either resistant to carbon formation/deposition or able to oxidize
the formed carbon. Fluorite oxides such as ceria or Ti-doped YSZ, and perovskites
such as doped lanthanum chromites or doped strontium titanates, have been sug-
gested as anode materials (2–4, 11, 12, 19). These materials are mixed conductors
at elevated temperatures under the conditions of the SOFC anode compartment.
The chromites have been evaluated in a stream of flowing methane with good
results in regard to stability; as for coke, only a limited formation of coke of two
to three monolayers is observed (11). The activity for oxidation of methane of the
chromites can be enhanced by doping with MgO, for example (20).

Electrochemical Oxidation of Carbon

The literature on electrochemical oxidation of carbon in aqueous solution is vast.
However only very little is known about the electrochemical oxidation of carbon
in an all solid-state reactor. In part this may be due to the fact that it is not easy
to perform the experiments, e.g., the addition of carbon in a continuous way is
difficult. Pioneering work by the Danish company Dinex Filter Technology A/S
on the electrochemical oxidation of carbon in a reactor constructed by porous
ceria and catalytic active electrodes has been reported (21). The work is carried
out as an attempt to clean up exhaust gas from diesel engines. It is claimed that
the oxidation of carbon is facilitated by the application of a potential across the
reactor. However, the work is carried out under net oxidizing conditions and not
in an environment that is similar to that of the anode compartment in a fuel cell.
Furthermore, the oxidation is not pure electrochemically because the process is
stated to be enhanced by the NEMCA effect (21) [for explanation of the NEMCA
effect see (22)]. However, ceria does prevent formation of carbon and/or oxidizes
it at low partial pressures of oxygen, as is found in the anode compartment of a
SOFC under operating conditions. One problem with the use of ceria is its volume
expansion during reduction from Ce4+ to Ce3+ (23). The reduced ceria expands
and peels off the electrolyte.

Direct Electrochemical Oxidation

As background information for this section, it should be mentioned that in order to
have a commercial potential, the area-specific internal resistance of the SOFC must
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not be higher than about 0.3–0.4 Äcm2. This means that the polarization resistance
of the anode should not be higher than about 0.2 Äcm2 at relevant SOFC anode
The direct electrochemical oxidation of methane in a SOFC was first reported
in detail by Steele et al. (1). It was observed that methane could be converted into
CO2 and H2O with good activity on oxide-based electrodes using Pt as a current
collector. Furthermore, it was reported that the oxidation on some electrodes was
only partial and that the selectivity depended on the composition of the electrode
material. The reaction rate was low, however, giving rise to high polarization
resistances. Ceria was also mentioned as a particularly good candidate for an anode
material for direct electrochemical oxidation of CH4 (2, 3). However, later detailed
investigations proved that reduced ceria is almost inactive to C–H bond breaking
(7, 24, 25). These findings are illustrated in Figures 2 and 3. The measurements
of Figure 2 are from the group at Imperial College (25), and we have added
the scales with current densities, assuming that each CH4 turnover releases eight
electrons. It is noted that the resulting limiting current densities are in the range
of 1 µA/cm2 in the temperature interval of 700–800◦ C. This corresponds to a
polarization resistance, Rp, in the range of 10 MÄcm2. Figure 3 shows the result
of an electrochemical measurement at 1000◦ C (7). A limiting current density of
around 0.1 A/cm2 was measured at overpotentials of 0.2 to 0.5 V. It was shown
by gas analysis that this current density corresponded well to the limitation of

Figure 2 Turnover frequencies for reaction of dry methane with gadolinia-doped

ceria and for steam reforming withn 5% methane/5.5% steam over gadolinia-doped
ceria. [After Aguiar et al. (25) with our additions of the current densities based on the
assumption of eight electrons per turnover.]
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Figure 3 Current density versus overpotential and electrode potential against a Pt/air
reference for a Ce0.6Cd0.4O1.8 (CG) electrode on an 8 YSZ electrolyte. pCH4 = 9 kPa,
pH2O = 3 kPa, bal. N2 1000◦ C, Au current collector [taken from Marina & Mogensen

hydrogen diffusion to the anode from a gas with low-hydrogen concentration. The
hydrogen originated from the cracking of CH4 in the test set-up.
In spite of the facts mentioned above, fast direct electrochemical oxidation of
hydrocarbons in SOFCs has been claimed in the recent literature by two groups:
one from Northwestern University (8, 26) and the other from the University of
Pennsylvania (9, 10, 27–34).
In the case of the work at Northwestern, an Rp below 1 Äcm2 at 650◦ C has
been demonstrated using relatively dry methane as fuel. A thin (2 µm) Ni/YSZ
anode is used, but a large improvement is achieved when adding a layer of YDC
((Y2O3)0.15(CeO2)0.85) between the YSZ electrolyte and the Ni/YSZ anode. The
electrode shows no sign of carbon formation after more than 100 h of operation.
The natural question here is, how can the Ni/YSZ anode be useful for the oxidation
of methane when it normally is destroyed within hours? It has been pointed out by
the authors that carbon formation is less pronounced at low temperatures because
no carbon is formed at the anodes operating at open circuit voltage (OCV) below
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700◦ C, whereas carbon formation is observed at temperatures above 700◦ C. This

is, however, in contrast to the fact that the rate of the formation of carbon is highest
at temperatures between 500 and 650◦ C (13, 35). No other investigations of the
Ni/YSZ anode for methane oxidation at intermediate temperature can confirm the
results by Barnett et al. (8). The YDC interphase layer is also shown to decrease
the rate of formation of carbon. Another point that must be raised is the low OCV
obtained by the authors (8), which is significantly lower than the potential predicted
from thermodynamics. This shows that equilibrium is not obtained at the anode.
Therefore, the potential is most likely a mixed potential or one with H2/H2O
ratio reflecting the amount (or rate) of methane being cracked. This indicates
that the reaction at the anode is proceeding either by internal reforming (due to
oxygen leakage through the electrolyte) or by cracking of methane followed by
electrochemical oxidation of the cracking products.
In the work at the University of Pennsylvania (10), both methane and higher
hydrocarbons have been tested as fuel in a SOFC with good results. The authors
use a copper-ceria composite electrode. No carbon formation is observed on the
copper-ceria-based electrodes after prolonged time in methane. Copper is claimed
to act as a current collector, and ceria is thought to act as an electrocatalytic material
in contrast to the findings shown in Figures 2 and 3. The ability of copper to form
C–C bonds is limited, which probably is the reason why no carbon is formed
on the electrodes. Copper cannot break the C–H bonds in methane. Ceria aids in
the combustion of carbon. Nonetheless, the OCV obtained by the authors is much
lower than the voltage predicted by thermodynamics, indicating that the conversion
of hydrocarbon is proceeding by a pathway other than by direct oxidation, i.e., by
cracking followed by electrochemical oxidation of the cracking products. In spite
of this, the results are very interesting. Gorte et al. has also used Ni-Cu-ceria
electrodes. An electrode containing Cu and Ni in the ratio 80%/20% (w/w) shows
an Rp as low as 1 Äcm2 at 800◦ C (33) after extended time in steam-humidified
methane. The electrodes were observed to improve during time owing to carbon
deposition, which improved the electronic conductivity of the electrodes. Copper
suppresses carbon formation; ceria combusts carbon and also suppresses carbon
formation. The results are in part confirmed by (36) but with much higher Rp
values, about 25 Äcm2 at 750◦ C. Also it is has been shown that the Rp values
are higher with the highest content of copper. However, the authors (36) did not
use ceria, which might explain the difference in the performance. Other authors
have investigated the oxidation of methane on different types of materials with poor
results, as seen from a technological point of view (37). An example of these results
is the use of lanthanum-chromites with different dopants, i.e., Ru. These chromites
showed very high Rp values. The chromites seem to be poor electrocatalysts and
are probably not adequate for use as anodes for the oxidation of methane in spite of
their high stability toward coking. Also, doped titanates have been investigated as
electrodes for the oxidation of methane, with a high Rp of 170 Äcm2 at 930◦ C (38).
In summary, interesting results have been obtained using humidified hydro-
carbons as fuel with ceria-based electrodes. This conversion of hydrocarbons
is probably not due to direct oxidation of methane but rather due to cracking
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followed by the oxidation of the cracking compounds. The use of ceria seems to
be a means for obtaining robust and highly active electrodes for the oxidation of

In a strict sense, direct electrochemical oxidation of hydrocarbon on mixed con-
ductors such as reduced and/or doped ceria does not occur with a reaction rate that
is of any technological interest. The high reaction rates/current densities reported
in several recent papers are instead based on a cracking of the hydrocarbons on
metals in the experimental set up or on homogeneous cracking in the gas phase,
followed by electrochemical oxidation of hydrogen and, in the case of ceria, prob-
ably electrochemical oxidization of carbon. A distinction should be made between
CH4, which is a fairly stable molecule that does not crack easily unless in the
presence of a metal cracking catalyst such as nickel, and the higher hydrocarbons,
which crack in the gas phase at temperatures of about 600◦ C.
The fact that ceria is very resistant to carbon precipitation is probably also of
great importance for maintaining the reactivity of the anode. Of further importance
is the fact that carbon formation does not take place on copper, which is not an
efficient methane cracker even at 900◦ C.
Even though the literature about direct conversion of hydrocarbon in SOFCs
seems promising, great care should be taken in the assessment of the possibility
of using untreated hydrocarbons as fuels in SOFC systems. The fact that dry
hydrocarbons are prone to cracking under SOFC conditions means that there is a
need for much more work to be done, both with respect to clarifying the conversion
mechanisms and with tests relevant to real SOFC technology.

This review was done as part of the Danish solid oxide fuel cell program, DK-
SOFCb, contract No. 1713/01-0001. The authors thank the Danish Energy Agency
for financial support.

The Annual Review of Materials Research is online at


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