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CONVERSION OF HYDROCARBONS IN
SOLID OXIDE FUEL CELLS
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
INTRODUCTION
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).
REFORMING OF HYDROCARBONS
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 ,
and
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.
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.
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
Polymerization
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).
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
conditions.
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 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
(7)].
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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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
hydrocarbons.
CONCLUDING REMARKS
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.
ACKNOWLEDGMENTS
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.
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