A Review of Anode Materials Development in Solid
A Review of Anode Materials Development in Solid
A Review of Anode Materials Development in Solid
High temperature solid oxide fuel cell (SOFC) has prospect and potential to generate
electricity from fossil fuels with high efficiency and very low greenhouse gas emissions as
compared to traditional thermal power plants. In the last 10 years, there has been significant
progress in the materials development and stack technologies in SOFC. The objective of
this paper is to review the development of anode materials in SOFC from the viewpoint of
materials microstructure and performance associated with the fabrication and optimization
processes. Latest development and achievement in the Ni/Y2 O3 -ZrO2 (Ni/YSZ) cermet
anodes, alternative and conducting oxide anodes and anode-supported substrate materials
are presented. Challenges and research trends based on the fundamental understanding of
the materials science and engineering for the anode development for the commercially
viable SOFC technologies are discussed. C 2004 Kluwer Academic Publishers
0022–2461
C 2004 Kluwer Academic Publishers 4405
sufficient electrocatalytic activity for fuel oxidation re- Internal reforming of hydrocarbon fuels is often ac-
actions, chemically stable and thermally compatible companied by carbon deposition. Carbon deposition
with other cell components and has sufficient poros- covers the active sites of the anodes, resulting in the
ity for efficient gas transportation in high-temperature loss of cell performance [32, 33]. High steam/carbon
reducing environment [2]. (S/C) ratios (e.g., up to 3) are typically used in con-
Due to the requirements of operating in reducing ventional steam reformers to suppress the carbon for-
environment and high electronic conductivity, pure mation. However, high S/C ratio is unattractive for fuel
porous metallic electrodes, in principle, can be used as cells as it lowers the electrical efficiency of the fuel
anode. Several metals such as Ni [15–17], Pt [17–19] cell by steam dilution of the fuel. The endothermic
and Ru [20] have been studied as anode materials. Se- nature of steam reforming reaction (Equation 2) can
toguchi et al. [21] studied the electrochemical activity cause local cooling and steep thermal gradients poten-
of Ni, Co, Fe, Pt, Mn and Ru and found that Ni exhibits tially capable of mechanically damaging the cell stack
the highest electrochemical activity for H2 oxidation re- [34]. Nevertheless, the impact of the endothermicity
action. Pure nickel has a melting point of 1453◦ C, a ther- of methane steam reforming process on the cell stabil-
mal expansion coefficient of 13.3 × 10−6 cm·cm−1 k−1 ity can be reduced by the combination of both exter-
and electronic conductivities of 138 × 104 S cm−1 and nal and internal reforming activity [35] or by using the
∼2 × 104 S cm−1 at 25◦ and 1000◦ C, respectively. Rel- so called gradual internal reforming (GIR) of methane
atively low melting temperature results in the tendency [36, 37].
of lower sintering temperature (1000◦ C) and the ther- Despite the excellent electrocatalytic properties of
mal expansion coefficient of Ni is much higher than that Ni/YSZ cermet materials for operation in H2 fuel,
of YSZ electrolyte (the thermal expansion coefficient Ni/YSZ based anode suffers a number of drawbacks in
of YSZ is in the range of ∼10.5 × 10−6 cm·cm−1 K−1 ). systems where natural gas is used as the fuel, notably
Addition of YSZ electrolyte phase into Ni significantly the sulfur poisoning and carbon deposition caused by
reduces the thermal expansion of the composite ma- cracking of methane. Under high carbon activity envi-
terial in order to be thermally compatible with the ronment iron, nickel, cobalt and alloys based on these
electrolyte [22, 23]. It is generally accepted that the metals could corrode by a process known as metal dust-
electrochemical activity of Ni anodes for H2 oxidation ing. Metal dusting involves the disintegration of bulk
reaction depends strongly on the three phase bound- metals and alloys into metal particles at high temper-
ary (TPB where fuel gas, Ni and YSZ phases are met) atures (300–850◦ C) in environment that are supersat-
areas [24–26]. De Boer et al. [27] observed the sig- urated with carbon. Ni corrosion process strongly de-
nificant reduction of electrode polarization resistance pends on the temperature and the gas composition and
of porous Ni electrode modified by deposition of fine in general Ni corrosion rate increases with tempera-
YSZ particle as compared to pure Ni electrode. This ture [38]. The form of carbon deposited on Ni in wet
indicates that YSZ phase in the cermet plays an impor- methane was found to be graphite as observed by in situ
tant electrocatalytic role in the creation of additional Raman microspectroscopy and the deposited carbon
reaction sites by extending the two-dimensional reac- cannot be burned by electrochemically permeated oxy-
tion zone into three-dimensional reaction zone, signif- gen [39]. There is also increased possibility for nickel
icantly enhancing the reaction kinetics in addition to oxidation at temperatures below 700◦ C as the result of
the inhibiting of the coarsening and grain growth of the increased partial pressure of oxygen under typical
the Ni phase [28–30]. Therefore the system of com- operating conditions [40]. The large volume change in-
posite anode usually consisting of metal-oxide cermet volved in the oxidation and reduction cycle of Ni/NiO
structure has been overwhelmingly accepted. Today, (theoretical density is 8.9 gcm−3 for Ni and 6.96 gcm−3
the Ni/Y2 O3 -ZrO2 (Ni/YSZ) cermet materials are still for NiO) could cause the instability of the Ni/YSZ cer-
the most common anodes for SOFC. met microstructure. The performance of conventional
Fuel cells that directly use hydrocarbon fuels such Ni/YSZ cermet anode is also not satisfactory at tem-
as natural gas, without first reforming those hydrocar- perature range of 500 to 600◦ C due to the low ionic
bons to hydrogen, will have enormous advantages over conductivity of YSZ phase in the cermet. Thus, the
conventional hydrogen-based fuel cells [31]. Remov- driving force for the development of alternative anodes
ing the need either to supply hydrogen to the fuel cell is mainly due to the need to replace Ni/YSZ cermet an-
or to include a hydrocarbon-reforming system greatly odes for the direct oxidation of hydrocarbon fuels such
decreases the complexity, size and cost of the fuel cell as methane and to develop dimensionally stable anodes
system. Natural gas is regarded as a relatively cheap and with high mixed electronic and ionic conductivity for
clean fuel. The advantage of SOFC over other fuel cells low temperature SOFC [41, 42].
is that the natural gas can be directly used without the The purpose of this paper is to review the achieve-
need to external fuel reformer and water-gas shift reac- ments and progresses in the development of Ni/YSZ
tor. The main component of natural gas is methane and based anode materials and alternative conducting ox-
following reforming reactions can take place directly ide anode materials in solid oxide fuel cells. Materials
inside a Ni/YSZ cermet anode: development for anode-supported structures is also re-
viewed. Emphasis will be placed on the development
and progress in the last 10 years. Finally the direction
CH4 + H2 O = 3H2 + CO (2)
and strategies in the development and optimization of
CO + H2 O = CO2 + H2 (3) SOFC anode materials are discussed.
4406
Figure 1 A generalized processing route for the preparation of Ni/YSZ cermet anodes.
2.1.4. Synthesis of cermet powders powder [63–65]. In this method, nitrate precursors
In addition to the conventional ceramic mixing process of the cermet constitutes such as ZrO(NO3 )2 ·6H2 O,
based on commercial NiO and YSZ powders, Ni/YSZ Y(NO3 )3 ·6H2 O and Ni(NO3 )2 ·6H2 O are mixed inti-
materials can also be prepared by other methods such mately, melted together with urea (CO(NH2 )2 ) on a hot
as wet chemical synthesis process. The purpose of the plate and the combustion takes place in a furnace pre-
synthesis of the Ni/YSZ cermet powders is primarily to heated at 600◦ C. Reported results showed that the spe-
improve the homogeneity of Ni and YSZ phase distri- cific area of Ni/YSZ powder with 50 vol% YSZ phase
bution, to reduce the sintering temperature of the cer- was 26 m2 /g and decreased to 17 m2 g−1 with the ad-
met coating and to increase the electrode performance dition of 2% Cu. The electrode polarization resistance
and stability. A major consideration in the synthesis of of a symmetrical cell was estimated to be 0.2 cm2 at
Ni/YSZ powders is the effect of the process on the pow- 1000◦ C, a reasonable value compared to those reported
der morphology and phase distribution. Millini et al. for optimized Ni/YSZ cermet anodes prepared by con-
[59] showed that the powder morphology of NiO/YSZ ventional powders [66]. Ni/YSZ cermet powders could
powders prepared by citrate route could change from also be prepared by mixed citrate/nitrate combustion
spherical shape by spray-drier to irregular aggregates by synthesis [67].
rotary evaporation. Li et al. [60] employed NH3 ·H2 O- Spray pyrolysis was used to prepare Ni/YSZ
NH4 HCO3 buffer-solution to co-precipitate Ni/YSZ composite powders from 8 mol% Y2 O3 -ZrO2 and
powder with improved homogeneity of the powder Ni(CH3 COO)2 ·4H2 O solution [68, 69]. The Ni/YSZ
composition and uniformity of the particle size. Us- powder obtained by this method showed spherical mor-
ing NaOH as the co-precipitation agent can avoid the phology with average particle size of ∼1 µm. The cer-
Ni loss, resulting in the accurate control of the cermet met anode prepared from the synthesized composite
composition [61]. Fine Ni/YSZ cermet powder with powder has good distribution of Ni and YSZ phases
surface area of 27–32 m2 g−1 and average particle size and the cell prepared from the Ni/YSZ cermet anodes
of 0.25–0.8 µm, prepared by solution combustion of ni- using the spray pyrolysis powder showed no deteriora-
trate salt and carbohydrazide fuel followed by hydrogen tion over 8000 h at 1000◦ C in moist H2 /air. The same
reduction at 800◦ C [62], have been reported. Combus- method was also used to prepare Ni/SDC cermet pow-
tion synthesis method is also commonly employed to der with Ce(NO3 )3 , Sm2 O3 and Ni(CH3 COO)2 ·4H2 O
produce Ni/YSZ and (Ni,M = Co,Fe,Cu)/YSZ cermet raw materials. Ni/SDC powder obtained by this method
4411
had average particle size of ∼0.5 µm and specific area 2.2. Electrical conductivity
higher than 2 m2 g−1 [70, 71]. Chung et al. [72] used In the Ni/YSZ cermet materials, YSZ is an ionic con-
gas atomization method to prepare Ni/CeO2 as poten- ductor and Ni is an electronic conductor. In a sim-
tial materials for internal reforming anodes. Gas atom- ple diphase system the theory predicts the percolation
ization can be defined as the break up of a liquid into threshold of ∼30 vol% of the higher conducting phase
fine droplets by the impringement of gas. The prod- for the transition from dominant ionic conductivity to
uct is a suspension of very fine liquid droplets which dominant electronic conductivity. This is generally true
then solidify very quickly. The rapid cooling intrinsic for the electronic conductivity of the composite Ni/YSZ
to gas atomization allows very little time for segre- cermet systems. Dees et al. [84] studied the relation-
gation to occur. Using intermetallic precursor, CeNi5 , ship between the electrical conductivity and the vol-
Chung et al. [72] produced Ni/CeO2 particles with grain ume fraction of Ni in the Ni/YSZ cermet measured at
size ranging from 5 µm to as large as 100 µm. How- 1000◦ C and showed that the rapid rise in the electri-
ever, the electrochemical performance of the anodes cal conductivity corresponds to a ∼30 vol% of Ni in
prepared from the gas atomized Ni/CeO2 powder was the cermet. However, the position of the S-shape de-
not as good as Ni/CeO2 anodes prepared by conven- pendence of the conductivity on the Ni volume content
tional ceramic mixing method. Chen and Liu [73] re- and the conductivity appear to be related to the particle
ported the preparation of mesoporous YSZ/NiO com- size of YSZ phase in the cermet, as shown in Fig. 9. In
posite with very high surface area of 108 m2 g−1 using general, the electrical conductivity of Ni/YSZ materials
Pluronic P103 surfactant as structure-directing agents increases with the YSZ particle size. The rather unusu-
and metal chlorides as precursors. Ultrafine Ni/YSZ ally smooth transition instead of S-shape threshold type
powder and nano-sized NiO and SDC powder can also for Ni/YSZ cermet prepared by self-propagating high
be prepared by sol-gel and liquid mixture methods [74] temperature synthesis (SHS) was attributed to the un-
and by heating the oxalate precursors at 300 to 1200◦ C usual microstructure and good dispersion of the metal-
in air [75], respectively. Gd-doped CeO2 (GDC) pow- lic component due to the very high temperature expe-
ders produced by metal nitrate-glycine process can be rienced during the SHS process [90]. The much lower
densified at temperatures as low as 1250◦ C and this threshold of conductivity for Ni/YSZ cermets prepared
led to the decrease in sintering temperature of the by using Ni-coated graphite (NiGr/YSZ) was due to the
Ni/GDC cermet anodes [76]. Moon et al. [77] reported large effective Ni content created by the thin Ni layers
the preparation of ZrO2 -coated NiO powder by thermal in the cermet [89]. This indicates that the electrical con-
hydrolysis of Zr(NO3 )2 ·6H2 O in a mixed solvent of ductivity of Ni/YSZ is closely related to the microstruc-
iso-PrOH/water. Using advanced mechanical method ture of the cermet. However, difference in percolation
in dry process can also produce YSZ-covered submi- threshold and conductivity may also be affected by the
cron NiO composite powders [78]. The presence of porosity as in conductivity curves shown in Fig. 9 level
fine YSZ particles on the surface of NiO would signifi- of porosity has not been taken into account.
cantly inhibit the grain growth of NiO phase in the cer- Electrical conductivity of Ni/YSZ cermets is strongly
met. Other methods employed to prepare Ni/YSZ cer- dependent on the particle size and distribution of both
met anodes include vapor-deposition [79], wet-powder Ni and YSZ phases and thus the threshold of the volume
spraying [80] and mechanical milling and plasma spray fraction of Ni in the cermet for the change of the con-
[81]. duction mechanism also changes. Huebner et al. [91]
Cracium et al. [82] reported a new method for the showed that with Ni average particle size of ∼0.6 µm,
fabrication of SOFC anodes. In this method, a porous the electrical conductivity reached ∼300 S cm−1 at
YSZ coating was formed using a mixture of YSZ pow-
der and YSZ fibers, followed by impregnation of the
porous YSZ coating with aqueous solution of Ni, or
Cu. Performance of the Ni/YSZ and Cu/YSZ cermet
anodes prepared by this method was comparable to
those of conventional Ni/YSZ cermet anode. The ad-
vantage of this method is the high freedom of adding
metal or other additives such as CeO2 to the cermet
structure. The feasibility of this method in the devel-
opment of Cu/ceria/YSZ cermet anodes for the direct
oxidation of methane has been demonstrated by Park
et al. [83].
However, considerations in the selection of the syn-
thesis of the Ni/YSZ cermet powders or simply to use
conventional ceramic mixing processes based on com-
mercial powders are the reproducibility, quality and the
cost of the process and raw materials. The issues asso-
ciated with the reproducibility are determined by the
Figure 9 Conductivity of Ni/YSZ cermet as a function of Ni content.
complexity of the synthesis processes while the cost of The conductivity was measured at 1000◦ C in humidified H2 . Numbers
the process is largely determined by the scale-up and are the references cited. The conductivity value for NiGr/YSZ cermets
automation. as reported by Corbin and Qiao [89] was measured at 800◦ C.
4412
1000◦ C for 30 vol% Ni and when particle size of Ni reduction in humidified H2 . An increase in the poros-
increased to ∼16 µm, the threshold volume fraction ity is clearly seen. In general, the porosity increases
of Ni to reach electrical conductivity of ∼100 S cm−1 with the increase in the Ni volume fraction and for
at 1000◦ C increased to 50 vol%. This indicates that Ni/8YSZ, a typical porosity of 35% was found for Ni
the threshold for the transition from the dominant ionic (40 vol%)/8YSZ (60 vol%) and 42% when Ni con-
conductivity of the YSZ electrolyte phase to the dom- tent increased to 70 vol% [86]. The porosity and pore
inant electric conductivity of the Ni metal phase is re- morphology can also be controlled by adding pore-
lated to the YSZ/NiO size ratio. The electrical conduc- formers such as carbon fiber, graphite and corn starch.
tivity of the Ni/YSZ cermet anodes is also dependent Addition of 10–20 wt% graphite pore-formers would
on the particle size and particle size distribution of NiO typically increase the porosity by ∼10% [49]. The
powders. Tietz et al. [45] studied the electrical conduc- porosity has strong effect on the electrical conductivity
tivity of the Ni/YSZ cermet anodes prepared from dif- through its impact on the Ni-to-Ni connectivity. There-
ferent commercial NiO powders. The electrical conduc- fore the electrical conductivity of the porous Ni/YSZ
tivity measured at 800◦ C varies between 300 S cm−1 to cermet coatings is expected to be considerably smaller
4000 S cm−1 with the highest conductivity obtained on than that of the Ni/YSZ cermet material. On a porous
NiO powder with small grain size and shrinkage rate Ni (50 vol%)/YSZ (50 vol%) cermet coatings screen-
of 27%. Tintinelli et al. [87] showed that the electri- printed on a 50 × 50 mm YSZ, the conductivity is ∼254
cal conductivity of Ni/8YSZ cermet anodes increases S cm−1 at 800◦ C in 97%H2 /3%H2 O, which is much
with increase of the 8YSZ/NiO particle size ratio. Itoh smaller than that of the dense Ni/YSZ cermet speci-
et al. [92] studied the relationship between the electrical men with similar volume fraction of nickel [93]. Ad-
conductivity and the particle size ratio of coarse YSZ dition of pore formers with geometric anisotropy such
(D50 = 10–100 µm), NiO (D50 = 1–100 µm) and fine as graphite and carbon fiber can result in the formation
YSZ (D50 = 0.4–60 µm). To achieve a good electrical of anisotropic porous structure of the Ni/YSZ cermets
conductivity, weight ratio (NiO/(coarse YSZ + NiO + [94, 95]. The electrical conductivity of Ni/YSZ with
fine YSZ)) of 8.8% or below is recommended. anisotropic porous structure is in the range of 150 to
For Ni/YSZ cermets to work properly as anodes, 600 S cm−1 as compared to ∼1600 S cm−1 for the cer-
certain porosity of the electrode coating is essential met with isotropic porous structure measured at 800◦ C
for the transportation of fuel gas reactants to the elec- [94]. This shows that porous structure also has signifi-
trode/electrolyte interface region where the fuel oxida- cant effect on the electrical conductivity of the Ni/YSZ
tion reaction occurs. The porosity is affected by vol- cermet anodes in addition to the porosity.
ume fraction of Ni in the cermet as there is a volume Conductivity of the Ni/YSZ cermet anode coat-
reduction of 25% when NiO is reduced to Ni metal ings in fuel cells is also affected by the heat treat-
under fuel environment. Fig. 10 shows the change of ment and sintering temperatures of the anodes. For Ni
the morphology of Ni anode before and after the NiO (50 vol%)/YSZ (50 vol%) cermet anodes prepared from
the cermet powder coarsened at 1400◦ C, the electri-
cal conductivity of the anode was only ∼4 S cm−1 at
1000◦ C for the anode sintered at 1300◦ C and increased
to ∼800 S cm−1 when the anode sintering temperature
increased to 1500◦ C [96]. The electrocatalytic activity
of the anodes for the H2 oxidation reaction also in-
creased substantially with the increase of the sintering
temperature of the anodes. The effect of sintering tem-
perature of Ni/YSZ cermets on the electrical conduc-
tivity behavior was also studied by Pratihar et al. [97].
Initial reduction temperature also affects the electrical
conductivity as reported by Grahl-Madsen et al. [98].
Electrical conductivity of Ni/8YSZ cermet substrates
was twice higher for the anode reduced at 1000◦ C than
that reduced at 800◦ C. On the other hand, the electri-
cal properties of two phase NiO-YSZ composites were
studied in the temperature range of 160–630◦ C by Park
et al. [99].
In comparison to electrical properties, relatively little
research has been carried out on the mechanical proper-
ties of Ni/YSZ cermets. Selcuk et al. [100] determined
the effective Young’s and shear moduli and Poisson’s
ratio of NiO/YSZ cermets as a function of porosity.
For 75 mol% NiO-YSZ thick specimen (∼550 µm)
sintered at 1350◦ C with porosity of 31%, the fracture
strength of NiO/YSZ is 56 MPa, which is close to
Figure 10 Change of the morphology of Ni anode before and after ex- 46 MPa of LSM but significantly smaller than 377 MPa
posure in humidified 10%H2 /90%N2 for 1 h at 1000◦ C. reported for dense YSZ [101, 102]. Primdahl et al. [58]
4413
qualitatively studied the effect of sintering temperature
of Ni/YSZ cermet anodes on the mechanical properties
of the YSZ electrolyte cells. Sintering at temperatures
of 1300 to 1400◦ C significantly reduced the mechan-
ical strength of YSZ electrolyte cell. However, high
temperature sintering of Ni/zirconia cermet anodes is
essential to reduce the electrode ohmic resistance and
electrode polarization resistance. This leaves little room
for the compromise of the optimum electrode perfor-
mance and cell mechanical properties. Sørensen et al.
[103] showed that fracture of the YSZ electrolyte is
most likely initiated by cracks growing from the cer-
met coating into the YSZ electrolyte. Nevertheless, the
residual stress in the NiO/YSZ anodes was much lower
as compared to that in LSM cathode due to stress relief
by the extensive channel cracking [104]. This explains
the observation that the applied load at failure and the
stress in the YSZ electrolyte for symmetrical NiO/YSZ
and YSZ structure was almost equal to that of YSZ
plates [104].
and this is also indicated by negligible change in the phase in the preparation of NiO/YSZ cermets through
morphology of the cermet coating (Figs 11b and 12c). effective milling and deagglomeration are also effective
This shows that microstructural stability of Ni/YSZ cer- in improving the stability of the anodes [113].
met anodes is critically dependent on the Ni content and Operating conditions of fuel cells also have signif-
Ni and YSZ phase distribution in the cermet. The uni- icant effect on the microstructure of the cermet an-
form distribution and homogenization of NiO and YSZ odes. Iwata [105] studied the microstructural change
4415
of Ni/8YSZ cermet electrode coatings operating at of CeGdO2 to the Ni cermet anodes was reported to
0.3 A cm−2 and 1000◦ C. Ni particle size increased from improve the redox stability of the cell [120].
0.1–1 to 1–10 µm after 1015 h of operation and the Antonucci et al. [121] studied the stability and per-
specific area of the cermets was decreased by half. The formance of Pt/CeO2 anode and Pt/PrO2 cathode of a
performance degradation rate was 14 mV over 1000 h. tubular SOFC stack. Significant chemical and morpho-
This was considered to be caused by the decrease of logical changes occurred in both anode and cathode
the contact area at the electrode/electrolyte interface after 3000 h operation at 950◦ C. There was a signif-
and a decrease of the specific surface area of Ni par- icant depletion of CeO2 and formation of Pt/Ce alloy
ticles. Müller [114] showed that high current and high on the anode side and a strong depletion of PrO2 on
fuel utilization can cause the agglomeration of origi- the cathode side, leading to the substantial change in
nally fine dispersed Ni in the Ni/YSZ cermet anodes. the reaction process and the degradation in the stack
The agglomeration of Ni phase in the cermet led to the performance.
reduction in the three phase boundary and the increase
in the polarization resistance of the anode [115].
While in principle it is evident that Ni particles will 2.4. Microstructure optimization
grow during high temperature operation, a detailed de- The performance of Ni/YSZ cermet anodes depends on
scription of the kinetics of the agglomeration and sin- the optimum phase distribution between Ni and YSZ
tering of the Ni/YSZ cermets is difficult due to the com- particles that ensurs the maximum electronic and ionic
plexity of the structure. Two types of materials (Ni and paths. Both modeling and experimental approaches are
YSZ) plus pores exist in the structure with all of them reported in the literature.
having multi-modal size distributions. Ioselevich et al.
[116] and Abel et al. [117] used correlated percolation
model to describe the degradation of SOFC anodes. In 2.4.1. Modeling approach
their model, monosized particles are located on a face- Modeling approach has been adopted by many re-
centered cubic lattice and sintering between two metal searchers for optimizing the performance of electrodes.
particles occur instantaneously with a certain probabil- It is known that the microstructure of the electrode plays
ity. The result is an unchanged particle and one pore or a critical role in determining the performance of the
one dead particle with no more electrochemical contri- electrodes, and thus the performance of the cell as a
bution to the network. The model gives an insight in the whole. An optimized microstructure of cermet elec-
development of active bonds in the anode, the density trode, for example, should have long-range connectiv-
of three phase boundaries and the transport resistance ity of respective ionic and electronic conductor chains
in anodic materials. A simple two-particles model was stretching across the electrode and linking the current
used by Vaßen et al. [118] to describe the degrada- collector to the electrolyte; and maximized active sites
tion of Ni/YSZ cermet anodes. The model is based on of three-phase boundary (TPB) for electrochemical re-
the assumption that the difference in particle size is actions. These requirements warrant an optimal ratio of
the driving force for the sintering of the large metal ionic to electronic conductors, in terms of their volume
particles and sintering mechanism is dominated by the and average grain size, in a properly sintered electrode.
surface diffusion of metal atoms. From the model, the In addition to the required microstructure for enhanced
surface diffusion coefficient of Ni on Ni surface was conversion of ionic to electronic current taking place at
1.3 × 10−12 m2 s−1 at 1000◦ C and a reasonable corre- the TPB and transport of these currents along their re-
lation of the grain growth of Ni particles was observed spective “active bond” (chains), there is other important
between the model and experimental data. consideration such as efficient gas diffusion from the
When a system breakdown happened, there would be bulk into the reaction sites. The latter warrants prop-
two scenarios for the anode side of the cell: either the erly design microstructure in terms of pore size and
reducing atmosphere is preserved with nitrogen (im- its distribution, porosity and the diffusion path. In sum-
plying nitrogen supply) or the cells stand a redox cycle. mary, a good electrode must consider the complex inter-
Thus, redox stability of anode materials is very impor- relationship among the microstructure, electrochemical
tant as the large volume change associated with NiO re- processes and gas transport phenomena. As one can see
duction to Ni may cause the disintegration of the cermet the complexity in designing an optimal electrode, mi-
structure. The mechanical strength of Ni/8YSZ sub- cro modeling is a useful approach for researchers to
strates before and after the reduction in hydrogen was achieve the goal, in particular to guide the design of a
reported to be similar, about 18–20 MPa [98]. However, high-performance electrode.
repeated reduction and oxidation at 1000◦ C weaken the Literature review showed that the electrode micro
mechanical strength of Ni/8YSZ membranes [119], in- model of SOFCs could roughly be divided into pore
dicating the dwindling of bonding between Ni-to-Ni model [122], random resistor network model [123–
and Ni-to-YSZ in the cermets. Grahl-Madsen et al. [98] 125], and random packing sphere model [126, 127].
showed that the redox cycle may have sped up the dete- In the pore model, the ionic conductor in the electrode
rioration of the electrical conductivity of the Ni/8YSZ is viewed as protruding from the dense electrolyte sur-
cermet substrates. This is supported by the significant face with electronic conducting particles spread over
increase of the electrode ohmic resistance of anode- the surface in a connected network and the remaining
supported cell after exposing the anode to mild oxida- space is filled by continuous pore structure for the trans-
tive conditions (normal grade N2 flow) [33]. Addition port of gases. In the random resistor network model,
4416
potential for H2 oxidation on wet H2 [128]. The pre-
dicted results show that for fixed particle radii of 0.1,
0.2 and 0.5 µm, the polarization reaches the minimum
at anode thickness of roughly 50, 100 and 160 µm, re-
spectively. Loselevich and Kornyshev [129] developed
a phenomenological model of cermet anode based on
a simple macro- and micro-kinetics of charge and gas
transport in the electrode. The model considered the
transport of hydrogen molecules and oxygen anions to
the reaction sites, hydrogen oxidation reaction and the
water-product removal.
Apart from above modeling approaches, Chan et al.
[130] has developed a complete polarization model for
SOFC and using it to study the sensitivity of perfor-
mance to the change of cell component thickness. The
Figure 13 Influence of particle size and anode thickness to the polar-
study revealed that, for the same materials used, same
ization for H2 oxidation (hydrogen humidified at 50◦ C, i.e., H2 :H2 O =
87.6:12.4) [128]. electrode kinetics and under same operating conditions,
the performance of a cathode-supported cell would be
the electrode is assumed to consist of grains of the no way better than an anode-supported cell even under
electronic conductors and the ionic conductors packed elevated feedstock pressure conditions. The study also
together so as to form a continuous network. In the ran- showed that reducing the thickness of all three princi-
dom packing sphere model, the electrode is assumed to pal components of the fuel cell (anode, electrolyte and
be a random packing of spheres. The theory of the par- cathode) could improve the operating current density
ticle coordination number was applied, together with range significantly.
the percolation theory. However, in this model [126,
127], the complex gas transport phenomena in the elec-
trode were ignored, despite its importance. Although 2.4.2. Experimental approach
concentration polarization does not play an important As shown by Primdahl and Mogensen [66], experimen-
role in most cases, especially for a thin anode, it does tally the relationship between the electrochemical per-
somehow affect the fuel cell performance significantly formance and microstructure of Ni/YSZ cermet anodes
if crucial parameters related to microstructure of the is rather complex. However, a general trend does exist
anode are not properly chosen. Chan and Xia [128] de- between the microstructure, the electrochemical behav-
veloped a micro model for the anode that formed by a ior and performance of the anode. Fig. 14 shows the
mixture of electronic and ionic conductors. The model electrochemical impedance arcs for four different an-
considers the complex inter-relationship among the mi- odes measured at 1000◦ C in 97%H2 /3%H2 O [131]. The
crostructure, electrochemical processes and gas trans- particle size of Ni and YSZ of fine and coarse cermet an-
port phenomena in the anode. Fig. 13 shows the effect odes was in the range of 0.5–3 µm and 3–5 µm, respec-
of particle size and anode thickness on the polarization tively (Fig. 14a and b). Ni particles in Ni paste anode
Figure 14 Electrochemical impedance curves measured at 1000◦ C and open circuit in wet H2 . Points are experimental data and lines are fitted data.
(a) fine cermet anode, (b) coarse cermet anode, (c) Ni paste anode and (d) Ni felt anode after Brown et al. [131]. Symbols are experimental results
and lines are fitted results by equivalent circuit.
4417
were ∼10 µm (Fig. 14c) while Ni felt anode consisted
of 50 µm diameter fibers (Fig. 14d). Ni/YSZ cermet
anode with fine Ni and YSZ particles and thus fine mi-
crostructure had the smallest overall electrode polariza-
tion resistance (RE = 0.19 cm2 at 1000◦ C, Fig. 14a)
and electrode polarization resistance increased as the
microstructure became coarser. For Ni felt electrode,
RE increased to 27.8 cm2 at 1000◦ C (Fig. 14d). The
relationship between microstructure and electrochem-
ical performance of Ni based anodes was also studied
by others [132, 133]. The electrode impedance behav-
ior showed strong dependence on the characteristics of
the anode microstructure.
The microstructure of Ni/YSZ cermet anodes in
turn depends on the development and optimization
of the fabrication processes as shown above. On the
other hand, due to high temperature processing, certain
changes in the microstructure of Ni/YSZ cermet an-
odes are inevitable. Fig. 15 shows typical microstruc-
ture changes of Ni (50 vol%)/3YSZ (50 vol%) cermet
anodes in various fabrication stages [134]. In the green
state (i.e., the stage of anode coating before sintering),
distribution of NiO and 3YSZ particles was very uni-
form and the particle size was extremely small, in the
range of less than 1 µm (Fig. 15a). Pores were also
very small. After sintered at 1400◦ C in air for 2 h, there
was clearly significant grain growth for both NiO and
3YSZ particles and increase of porosity (Fig. 15b). In
comparison, the grain growth of NiO was substantially
higher than that of 3YSZ particles. Before the use as
fuel electrodes, NiO in the Ni/3YSZ cermet anode must
be reduced to Ni under fuel reducing environment. The
volume reduction of 25% in the reduction of NiO to
Ni metal leads to further increase in porosity and more
importantly there was further grain growth of Ni at oper-
ating temperature of 1000◦ C due to the poor wetability
between Ni and zirconia (Fig. 15c). Ni particles were
typically in the range of 2 to 5 µm and there was a sig-
nificant variation in the distribution between fine 3YSZ
particles and large Ni particles. In some cases, Ni par-
ticles were almost standing alone with little coverage
of zirocnia particles. This clearly demonstrates that the
sintering and reducing stages at high temperatures play
an important role in the formation of the microstructure
of Ni/zirconia cermet electrodes.
Ion impregnation was reported to be effective in
improving the microstructure of Ni/YSZ cermet an-
odes during the high temperature sintering and reduc- Figure 15 Microstructure evolution of Ni (50 vol%)/3YSZ (50 vol%)
cermet anodes in various fabrication stages of (a) green state, (b) after
ing processes [134]. In this method, metal ions usu- sintered at 1400◦ C, and (c) after reduction at 1000◦ C in wet H2 .
ally in nitrate solution such as Y0.03 Zr0.97 (NO3 )x or
Sm0.20 Ce0.80 (NO3 )x was impregnated into semi-fired or
as-fired Ni/YSZ cermet anode coatings, followed by de- and Fig. 17 shows the corresponding electrode perfor-
composition at high temperatures (i.e., fuel cell operat- mance measured in 97%H2 /3%H2 O at 800◦ C [134].
ing temperatures). As a result, nano-sized Y0.03 Zr0.97 O2 After impregnation treatment, Ni particle size was sub-
and Sm0.2 Ce0.8 O2 particles would deposit on the sur- stantially reduced and majority of Ni particles were
face of Ni and YSZ grains. The formation of fine oxide below ∼2 µm. Furthermore, Ni and YSZ particles
particles inhibits the sintering, grain growth and ag- were covered by very fine oxide particles. As shown
glomeration of zirconia and in particular Ni phases dur- in Fig. 17, polarization losses of impregnated Ni/8YSZ
ing sintering and reducing stages at high temperatures. cermet anodes were significantly reduced as compared
Fig. 16 shows the SEM pictures of Ni/8YSZ cermet an- to those without impregnation. For H2 oxidation on
odes before and after the ion impregnation treatment of Ni/8YSZ cermet anode without impregnation, η was
Sm0.2 Ce0.8 (NO3 )x nitrate solution after fuel cell testing, 234 mV at 250 mA cm−2 and 800◦ C. After impregnated
4418
Figure 16 SEM pictures of Ni (50 vol%)/8YSZ (50 vol%) cermet anodes with and without impregnation after fuel cell testing. (a) none, (b)
impregnation with 3 M Y0.03 Zr0.97 (NO3 )x , (c) impregnation with 3 M Sm0.2 Ce0.8 (NO3 )x and (d) impregnation three times with 3 M Sm0.2 Ce0.8 (NO3 )x
nitrate solution.
4419
Using electrochemically active interlayer to en-
large the reaction sites for the reaction at the elec-
trode/electrolyte interface has proved to be effective in
the promotion of the electrocatalytic activity of both an-
odes and cathodes. Mixed ionic and electronic conduct-
ing materials such as doped CeO2 are often used as the
interlayer [139]. The interlayer layer can also be used
to prevent the interfacial reaction between the electrode
and the electrolyte in some cases. Combining an inter-
layer of SDC and impregnated Ru catalysts, the current
density achieved at −0.9 V on modified SDC anode
structure was more than 4 times higher than that without
the interlayer and Ru additives [140]. Using a 0.5 µm
thick Y-doped ceria (YDC) interlayer between anode
and electrolyte, the electrode polarization resistance for
Ni/YSZ anode for methane oxidation was ∼1.2 cm2 Figure 18 Partial list of the electrode polarization resistance (RE ) of
at 600◦ C, which is much smaller than 6.6 cm2 for Ni/YSZ cermet anodes measured under moist hydrogen at different tem-
the Ni/YSZ cermet anode without the interlayer under peratures. RE was measured by electrochemical impedance spectroscopy
the same conditions [41]. Using double anode struc- at open circuit potential. Numbers are the references cited.
ture with electrochemically active, composite anode or
Ni/YSZ cermet anode with different Ni content and mi- offer an effective way to produce high performance and
crostructure as anode function layer, polarization per- high stable Ni/YSZ cermet anodes.
formance and power density increased as compared to Fig. 18 is the partial list of the electrode polarization
single anode layer structure [8]. The double layered an- resistance (RE ) of Ni/YSZ cermet anodes measured un-
ode showed good long-term stability [85]. Multilayer der moist hydrogen at different temperatures. RE was
anode concept with gradients in composition and mi- measured under open circuit potential by electrochem-
crostructure to function as electrochemical active layer, ical impedance spectroscopy and was obtained by the
gas diffusion layer and current collector top layer have difference of low and high frequency intercepts on the
also been proposed [141]. Müller et al. [142] showed impedance plots. Most of the results reported in the lit-
that such multilayer anode structure improved the po- erature are in the medium to high temperature range
larization performance and long term stability. (800 to 1000◦ C) and have wide variations in the RE
Limitations of the fabrication processes based on value. By extrapolating the results to low temperature
the conventional ceramic powder mixing process (see region, the electrode polarization resistance would be
Fig. 1) are the difficulties in achieving optimum phase in the range of 1–30 cm2 at 700◦ C and 7–200 cm2
distribution between Ni and YSZ particles. Several at 600◦ C for Ni/YSZ based anodes. The electrode po-
techniques have been developed to achieve better dis- larization resistance is still too high for H2 oxidation
tribution between Ni and YSZ for the preparation of reaction at temepratures below 700◦ C. However, with
cermet anodes for solid oxide fuel cells. The most no- modification of Ni/YSZ cermet anodes and with inco-
table one was based on electrochemical vapor deposi- poration of YDC interlayer, electrode polarization re-
tion (EVD) developed by Westinghouse [143]. In West- sistance as low as 0.26 cm2 at 600◦ C in wet H2 was
inghouse tubular cells, the anode is fabricated by slurry reported [41].
coating of nickel and YSZ is incorporated into the Ni
skeleton structure by EVD method. The morphology
of YSZ intergrowth restricts grain growth and sinter- 3. Modified Ni/YSZ cermet anodes
ing of Ni particles and provides an effective pathway Conventional Ni/YSZ cermet materials with and with-
for oxygen ions from YSZ electrolyte to Ni phase [12]. out catalyst modification have been extensively studied
Other deposition techniques reported include sputter- for the internal reforming of methane. The internal re-
ing [144], chemical vapor deposition (CVD) [145], a forming activity of the anodes is important as it converts
combined EVD/CVD process [145], polarized elec- methane into more electrochemically active species of
trochemical vapor deposition (PEVD) [146, 147], etc. H2 and CO. Unlike polymer electrolyte fuel cells, CO is
Each of these methods offers advantages in certain as- also a fuel for SOFC. However, the electrochemical ac-
pects but each also presents its own difficulties in terms tivities of Ni/YSZ cermet anodes for the CO oxidation
of cost, reproducibility, scale-up and microstructure reaction are much lower as compared to that of the an-
control. The objective in the development and optimiza- ode for the H2 oxidation reaction [150, 151]. Lee et al.
tion of a preparation process of Ni/YSZ cermet anodes [152] studied internal reforming reaction on Ni/YSZ
is on controlling and tailoring the electrode microstruc- cermet anodes with wide range of porosity and various
ture to certain degree and thus producing an anode not Ni content. The reaction is of first order with respect
only with high performance and stability but also with to the methane and −1.25 for the steam. Ahmed et al.
high reproducibility and low cost. The fabrication pro- [153, 154] studied the kinetics of internal reforming
cesses based on cheap and conventional ceramic pow- reaction on Ni/YSZ cermet anodes. On conventional
der mixing method in conjunction with microstructure Ni/YSZ cermet anodes, a steam/carbon (S/C) ratio of
improvement processes such as ion impregnation may 2 or higher was required to avoid carbon deposition. At
4420
steam/carbon ratios of 1.5–3, the rate of reforming re- [169, 170] shows that Ru and Pt addition promotes the
action is 0.84 order with respect to the partial pressure reforming activity and supress the carbon deposition.
of CH4 and −0.35 order with respect to the steam on The steam reforming reaction and carbon deposition are
conventional Ni/YSZ cermet anodes at temperatures of also reported by Onuma et al. [171] on Pt electrodes and
∼900◦ C. The activation energy of the reforming reac- Horita et al. [172] on Ni/YSZ and Fe/YSZ anodes. Sato
tion was 95 kJ mol−1 on Ni/YSZ cermet anodes. Ac- et al. [173] studied Ni-Co alloy/YSZ cermet anodes for
tivation energy values of 58 to 82 kJ mol−1 were also the oxidation of H2 and CH4 . Ni-Co alloy was prepared
reported for the steam reforming reaction on Ni/YSZ by co-precipitation, followed by sintering at 1100◦ C for
cermet anodes [155, 156]. High activation energy of 24 h. Co content in Ni-Co/YSZ anodes has little effect
118–294 kJ mol−1 was reported for the reforming re- on the cell performance with H2 fed but increases the
action on Ni/YSZ cermet anodes with addition of cata- cell performance with CH4 fed. The best composition
lyst such as Ce [157, 158]. Addition of small quantities was found to be Ni0.5 Co0.5 /YSZ. The increased activ-
of molybdenum (∼1%) was reported to significantly ity of Ni-Co/YSZ cermet anodes for CH4 oxidation was
reduce the carbon deposted on Ni/YSZ anode during explained by the preferential crystal orientation along
mechane reforming [159]. Drescher et al. [160] stud- (111) plane at the alloy surface, which was not observed
ied the reforming activities and structural properties for pure Ni powder. The exposure of the most densely
of Ni/8YSZ cermet substrates using temperature pro- packed plane in the face-centered cubic structure could
grammed reduction (TPR), gas adsorption, diffusion contribute to the formation of surface active sites for
and permeation measurements. The methane conver- the electrochemical oxidation of methane. Ni-Co/YSZ
sion rate increased linearly with the increase of anode cermet anodes achieved lowest electrode polarization
thickness up to 0.6 mm. The gas adsorption experiments resistance as compared to that of Ni-Cu/YSZ and Ni-
showed that the active Ni surface area is about 20% of Fe/YSZ cermet anodes for H2 oxidation reaction in wet
the total surface area of the cermet. TPR result indicates H2 [174]. Kim et al. [175] studied the carbon deposi-
that the Ni in the cermet would be completely reduced tion and CH4 oxidation on Ni-Cu alloy/YSZ cermet
at a temperature of about 500◦ C at sufficient hydrogen anode prepared by ion impregnation of porous YSZ
supply. This temperature range is close to those reported layer with copper and nickel nitrite solution. Carbon
by Perego et al. [161] and Shirakawa et al. [162]. was found to deposit on Ni-Cu alloy. However, for Ni-
The effect of carbon deposition on the electrochem- Cu alloy/YSZ cermet anodes with low Ni content such
ical activity of Ni/YSZ cermet anodes in the methane as Ni0.2 Cu0.8 /YSZ, small amount of carbon deposition,
fuel appears to be related to the operating conditions in fact, could promote the cell performance, similar to
such as current load. Koh et al. [33] showed that at open that of pure Cu/YSZ cermet anodes [176]. On the other
circuit or low current density, the effect of carbon depo- hand, it was reported that there was no carbon deposi-
sition on the electrocatalytic activity of Ni/YSZ cermet tion on Ni0.52 Cu0.48 /GDC cermet anodes prepared from
anodes was irreversible. Conversely, under high current very fine Ni0.52 Cu0.48 alloy after operating in dry CH4
load, the polarization performance of the Ni/YSZ was for ∼40 h at 800◦ C [177]. Carbon deposition was also
reversible. This indicates the possibility of minimiza- found on Ni0.8 Mg0.2 /YSZ cermet anodes after exposure
tion of the carbon deposition on Ni/YSZ cermet anodes. to wet methane [178]. Electrode polarization resistance
Weber et al. [163] demonstrated the stability of Ni/YSZ for the reaction in wet methane on Ni0.8 Mg0.2 /YSZ an-
cermet anode up to 1000 h under a current density of ode was 9.2 cm2 at 1000◦ C, which is much higher
0.4 A cm−2 at 950◦ C in dry methane without serious than 1.7 cm2 in wet H2 .
degradation in performance. Presence of sulfur (primarily in the form of H2 S) in
Under high current and low concentration (4–9%) of the fuel gas can also affect the performance of Ni/YSZ
dry methane, methane was reported to be completely cermet anodes. Geyer et al. [179] reported that the
oxidized to CO2 and H2 O without carbon deposition on electrode polarization resistance increased by a factor
Ni/YSZ cermet anodes [164, 165]. Under fuel cell oper- of two by additing only 5 ppm of H2 S at 950◦ C in
ation conditions where methane concentration was high 97%H2 /3%H2 O. Matsuzaki and Yasuda [180] showed
and current was lower than the threshold value, carbon that the poisoning effect of sulfur-containing fuel gas
deposition occurs at steam to carbon (S/C) ratio lower on the electrode performance depends on the total sul-
than 1 [166]. Liu and Barnett [167] studied the perfor- fur content and the temperature. The tolerance of the
mance and stability of Ni/YSZ anode-supported SOFC anode towards sulfur poisoning increased with the in-
operated with wet methane and natural gas at 600– creasing operation temperature. Study showed that for
800◦ C. Under a current density of ∼0.6 A cm−2 , the a sulfur content of 0.02 to 15 ppm, the performance loss
cells showed good stability with limited carbon depos- caused by the sulfur poisoning could be recovered after
tion. Takeguchi et al. [168] studied the carbon deposi- switching to the sulfur-free hydrogen fuel. The effect
tion and steam reforming of methane on Ni/YSZ anodes of sulfur impurities on the electrochemical activities of
modified with alkaline earth addition of MgO, CaO, Ni/YSZ cermet anodes was also studied by others [181,
SrO and CeO2 . CaO, SrO and CeO2 addition suppressed 182].
the carbon deposition while MgO addition promoted
the carbon deposition rate and decreased the steam re-
forming activity of the anodes. High content (∼2 wt%) 4. Other metal/oxide cermet anodes
of SrO and CeO2 in the Ni/YSZ cermets also reduced Instead of modifying Ni/YSZ cermet anodes, in-
the steam reforming activity significantly. Further study vestigations were also performed on the use of
4421
electronic or mixed conducting oxides to make alter- electrolyte and Sm0.5 Sr0.5 CoO3 cathode. On the other
native metal/oxide cermets such as ceria stabilized zir- hand, in a conventional SOFC configuration, a power
conia (CeO2 -ZrO2 ), calcium-doped ceria (Ca-CeO2 ), density of 0.192 W cm−2 was reported on Ni/SDC in
yttria-doped ceria (YDC), praseodymium oxide (PrOx ). wet CH4 , using similar electrolyte and cathode materi-
Mixed results were reported. Kawada et al. [151] stud- als [192].
ied Ni cermets prepared from CeO2 -ZrO2 , Ca-CeO2 , The chemical compatibility between YSZ and ce-
and Y-CeO2 and showed no significant improvement in ria has been studied by Tsoga et al. [193, 194]. Gd-
the electrode performance as compared to Ni/YSZ an- doped ceria (GDC) and YSZ react and diffuse into each
odes. Relatively high overpotential and high resistance other during sintering process at 1200◦ C, forming Gd
were also observed for ceria related Ni cermet anodes. rich phase with ionic conductivity two orders lower
Eguchi et al. [183], on the other hand, reported the sig- than that of YSZ at 800◦ C [194]. Further study [195]
nificant improvement in the polarization performance shows that the solid state reaction between YSZ and
of Ni cermets using samaria-doped ceria (SDC), CeOx GDC can be effectively suppressed with an interlayer
and PrOx (Ni/oxide ratio was 8/2 in weight) as com- of Ce0.43 Zr0.43 Gd0.10 Y0.04 O2 . Chemical compatibility
pared to Ni/YSZ anodes. The activity of the Ni/oxides is important for the long-term stability of the multi-
cermet for hydrogen oxidation was found to be in the layered structure where doped-ceria is often used as
following order interlayer on the cathode side [196] and anode side
[41] to protect and to enhance the cell performance. A
Ni/YSZ < Ni/CeOx < Ni/SDC < Ni/PrOx Ni (40 vol%)/GDC (60 vol%) composition is recom-
mended for the suppression of the reactivity between
The improved performance was attributed to the in- GDC in the Ni/GDC cermet anode and YSZ electrolyte
crease of the effective reaction area due to the ionic as the presence of Ni can inhibit the reactivity between
conduction of the oxides. Wang and Tasumi [184] in- YSZ and ceria [194].
dicated that addition of SDC to Ni anodes led to the Zhang et al. [70] and Ohara et al. [197] studied the
increase in activation energy and resulted in high over- effect of sintering temperature on the electrode perfor-
potential for H2 oxidation reactions on Ni/SDC anodes mance of Ni/SDC anodes on La0.9 Sr0.1 Ga0.8 Mg0.2 O3
at low temperatures. (LSGM) electrolytes. The best electrode performance
Joerger and Gauckler [185] studied the Ni/Gd-doped (overpotential of 30 mV at 300 mA cm−2 and 800◦ C)
CeO2 (Ni/GDC) cermet for H2 and CH4 oxidation re- was obtained on the anode sintered at 1250–1300◦ C
action. Ni/GDC cermet anodes were sintered at 1350◦ C with Ni content of ∼60 vol%. Sintering at 1350◦ C sig-
similar to that of Ni/YSZ cermet anodes. The electrical nificantly increased the electrode ohmic resistance and
conductivity of Ni/GDC anodes was 1.7 × 104 S cm−1 polarization overpotentials, which have been attributed
and electrocatalytic activity of Ni/GDC cermet was by the significant sintering of the Ni/SDC electrodes
much higher than that of Ni/YSZ cermet anodes. At and the Ni diffusion into the LSGM electrolyte phase.
800◦ C and 0.5 A cm−2 , η of Ni/GDC anode was Kuroda et al. [198] studied the electrode performance
∼20 mV for H2 oxidation reaction, significantly lower of Ni/SDC anodes on La0.8 Sr0.2 Ga0.8 Mg0.15 Co0.05 O3
than ∼120 mV obtained on Ni/YSZ cermet anodes. (LSGMC) at 650◦ C and found that the cell polarization
When using methane, η of Ni/GDC anode was ∼75 mV were dominated by the loss at the anode. High sensi-
at 800◦ C and 0.25 A cm−2 . Activation energies for tivity of the sintering temperature of the performance
the H2 and CH4 oxidation reaction was also lower on of Ni/SDC cermet anodes on LSGM electrolyte was
Ni/GDC anodes than those on Ni/YSZ anodes, exhibit- also observed by Huang et al. [199]. It has been shown
ing the catalytic and electrocatalytic activities of ce- that the formation of resistive phase of LaSrGa3 O7 ,
ria for the reforming and oxidation of hydrocarbons LaSrGaO4 or LaNiO3 between LSGM, NiO and SDC
and hydrogen. Lower overpotential was also reported is the main cause for the sensitivity of sintering tem-
on Ni/Sm-doped ceria (Ni/SDC) anode as compared to perature of the cermet anodes [199–202]. A Ni-free
Ni/YSZ anodes for H2 oxidation at 850◦ C [186] and the interlayer such as doped-CeO2 between LSGM and
best performance was found on Ni/SDC with 50 vol% Ni-based anodes could prevent the interfacial reaction
Ni content [187]. On Ni/GDC and Ni/15 mol% Y2 O3 - [199]. Power density close to 0.9 W cm−2 was reported
Ce0.7 Zr0.3 O2 anodes operated below 750◦ C, no carbon for a 600-µm thick LSGM electrolyte cell at 800◦ C,
deposition was found when dimethyl ether (DME) was using Ni/La2 O3 -doped ceria as the anode [199].
used as the fuel [188]. On the other hand, carbon de- Ni/Ti-doped YSZ cermets were also considered as
position was found on Ni/GDC anodes with 70 wt% the anodes for high temperature SOFC [203] due to the
Ni after operating on wet methane at 850◦ C for about attraction of mixed conductivities of TiO2 -doped YSZ
80 h [189]. With 5 wt% addition of Ru to Ni/GDC an- under low partial pressure of oxygen [204, 205]. Elec-
odes, the electrode polarization resistance to CH4 fuel trical conductivity of YSZ decreased with Ti doping
was reported to be 0.13 cm2 and a power density of in YSZ but the bending strength of T-doped YSZ in-
0.75 W cm−2 was recorded in dry CH4 at 600◦ C [190]. creased. The overpotential of 60 mV at 300 mA cm−2
Hibino et al. [191] also investigated Pd-doped Ni/SDC and 1000◦ C appeares to be compatible with those re-
cermet anodes for partial oxidation of CH4 . With a ported for Ni/YSZ cermet anodes.
small addition of Pd (7 wt% PdO), a maximum power Gorte and co-workers [42, 82, 83, 175, 206–208]
density of 0.644 W cm−2 at 550◦ C was achieved on a focused their efforts on the development of Cu/CeO2 /
single-chamber SOFC in CH4 /air mixture, using SDC YSZ based anodes. Unlike Ni, copper is inert to
4422
hydrogen or hydrocarbon oxidation and has no catalytic should be in direct contact with YSZ electrolyte for it to
activity for the formation of C C bonds, thus suppress- be effective [212]. Because Cu2 O and CuO melt at 1235
ing the carbon deposition [209]. The primary function and 1326◦ C, respectively, it is not feasible to prepare
of copper in the cermet anodes is to provide electronic Cu/YSZ cermets by high temperature sintering as those
conduction path. The melting point of Cu is 1083◦ C, used for Ni/YSZ cermet anodes. An alternative method
lower than 1453◦ C for Ni. Thus Cu-based anodes are was developed for the preparation of Cu/YSZ cermet
suitable for operating temperatures <800◦ C. However, anodes in which a porous YSZ was produced by acid
pure Cu/YSZ anode has very low electrochemical ac- leaching Ni from Ni/YSZ cermets, followed by addi-
tivity for both H2 and CH4 oxidation reactions. Ce- tion of Cu and catalysts such as ceria by impregnation
ria catalyst was added to Cu/YSZ cermet to improve [175, 213].
the electrode activity [83, 210]. The cells were oper- Ruthenium has high melting point (2310◦ C) as com-
ated with dry hydrocarbons including methane, butane pared to Ni (1453◦ ), thus providing better resistance
and synthetic diesel without any carbon deposition. A to sintering and grain growth. Ru/YSZ cermet anodes
power output of ∼0.15 W cm−2 at 700◦ C was observed show high catalytic activity for steam reforming and
in pure C4 H10 for a cell with a Cu/CeO2 /YSZ anode negligible carbon deposition under internal reforming
and a 60 µm thick YSZ electrolyte. Electrode perfor- conditions [214]. Vernoux et al. [215] also reached the
mance of Cu/CeO2 /YSZ anodes was significantly im- same conclusion. But its use is prohibited by the high
proved after exposed to hydrocarbon fuels in particular cost and evaporation above 1200◦ C to produce volatile
for the anode with Cu content lower than 30 vol%. RuO4 species.
This was explained by the effect of the hydrocarbon
deposits on the improvement of conductivity of the an-
ode, as shown schematically in Fig. 19 [211]. The effect 5. Conducting oxides
of lanthanide additives on the Cu/YSZ cermet anodes Mixed ionic and electronic conducting oxides such as
was also studied, but the performance of Cu/YSZ an- gadolinium- or samarium-doped ceria have been inves-
odes with lanthanide additives was not as good as that tigated as potential anode materials for intermediate
of Cu/ceria/YSZ cermet anodes [212]. In the case of temperature SOFC. The major attraction of such mixed
Cu/YSZ based anodes, the oxide catalyst such as ceria ionic and electronic conduction oxides is the possibility
of enhanced reaction zone over the three phase bound-
ary due to the high electronic conductivity as compared
to conventional YSZ. For example, the oxygen ion con-
ductivity of Sm-doped CeO2 is ∼0.1 S cm−1 at 800◦ C
is about four times higher than that of YSZ while its
electronic conductivity is ∼4 S cm−1 under H2 reduc-
ing environment [216, 217]. The ceria-based oxides,
titanate based oxides, and lanthanum chromite based
oxides will be discussed briefly below.
4425
Sr and Mn substitution would maintain the stability of plete oxidation to CO2 and H2 O by partial methane
the perovskite while other substitutes would destabi- dissociation (mainly involving surface adsorbed oxy-
lize the system. However, transitional metal substituted gen), and methane dissociation (mainly involving mo-
LaCrO3 did not decompose easily under reducing con- bile lattice oxygen) to form H and C species on
ditions, indicating that the decomposition of substituted the oxide surface. Methane dissociation was predom-
LaCrO3 would be hindered kinetically. Ca and Sr sub- inant at high temperatures (900–1000◦ C) with carbon
stitution at the A-site improves the catalytic activity and deposition.
for B-site substitution, Co and Mg showed an inhibit- Primdahl et al. [266] studied the electrocatalytic
ing effect while Mn, Fe and Ni improved the activity. activity of (La,Sr)CrO3 for H2 and CH4 oxidation
La0.75 Sr0.25 Cr0.5 Fe0.5 was shown stable under reduc- at 850◦ C. In the case of La0.8 Sr0.2 Cr0.97 V0.03 O3 , the
ing atmosphere but its electrochemical performance in electrode polarization resistance (RE ) was ∼5 cm2
wet methane was reported to be very poor [262]. Con- for H2 and ∼30 cm2 in CH4 with 3%H2 O at
sidering the catalytic activity and cracking resistance, 850◦ C. The presence of second phase formation in
(LaSr)(CrNi)O3 with 10% Ni doping was suggested La0.8 Sr0.2 Cr0.97 V0.03 O3 led to the formation of SrZrO3 .
to be most suitable for methane oxidation reactions This indicates that Sr-doped LaCrO3 has poor electro-
[263]. On the other hand, Ni exsolution has been found catalytic activity for H2 oxidation and shows little cat-
in 10% Ni-doped lanthanum chromites in fuel envi- alytic activity for direct CH4 oxidation. This is similar
ronment [264] and the surface segregation of Ni from to the previous reports on the overall low electrode per-
Ni-doped lanthanum chromites may be responsible for formance of steam reforming and direct methane ox-
the high activity. Liu et al. [265] showed that addition idation reaction on LaCrO3 and doped LaCrO3 [246,
of 5% NiO in La0.8 Sr0.2 Cr0.8 Mn0.2 O3 (LSCM)/GDC 267–269]. Chromite/titanate based perovskite anodes
(50 wt%/50 wt%) composite anodes significantly en- generally show much poorer electrochemical activity
hanced the anode activity for both H2 and CH4 oxida- for H2 oxidation as compared to that of Ni/YSZ cermet
tion. The power density of the cell with LSCM/GDC- anodes despite some of the perovskites have reason-
NiO anode was 0.13 W cm−2 at 750◦ C, much higher ably high electrical conductivity. This may be partially
than 0.05 W cm−2 on the cell with LSCM/GDC an- due to the poor adhesion between the perovskite coat-
ode without NiO addition. Enhancing effect of addit- ing and YSZ electrolyte [270]. Insertion of Ru or Mn
ing small amount of catalysts such as Ni and Ru on the into the B-site of LaCrO3 was shown to increase the
performance of LaCrO3 -based for fuel oxidation reac- electrochemical activity for the H2 oxidation as com-
tions was also studied by others [37, 266]. The amount pared to Sr-doped LaCrO3 [271]. The catalytic activity
of metal catalysts may be low enough to avoid carbon of Ru and V-doped (LaSr)CrO3 for steam reforming of
deposition [265]. methane was studied in detail as function of stream to
Middleton et al. [245] studied the activities of carbon ratio at 850◦ C [272]. It was pointed out that the
La0.8 Ca0.2 CrO3 for the CH4 conversion and oxidation Sr doping is the key factor in the stability of ruthenium
reactions. The oxide showed no significant formation in the chromite perovskite structure [273]. Recently Tao
of C2 compounds, but was the most active and selective and Irvine [274] reported some promising results of
catalyst for CO2 formation, with complete conversion La0.75 Sr0.25 Cr0.5 Mn0.5 O3 (LSCM) as anode for SOFC.
below 500◦ C, as compared with titanate-based oxides LSCM is a p-type conductor with conductivity of
[245]. At temperature above 800◦ C, the conversion of ∼38 S cm−1 at 900◦ C at oxygen partial pressure
methane dramatically increased, with the concomitant above 10−10 atm. The electrode polarization resistance
formation of CO and hydrogen. The methane reaction for the oxidation reactions in wet CH4 and H2 at
was suggested to occur in two separate ways, i.e., com- 900◦ C was 0.85 and 0.26 cm2 , respectively. Fig. 21
Figure 21 Performance of the cell with (La0.75 Sr0.25 )0.9 Cr0.5 Mn0.5 O3 anode and LSM cathode measured at different temperatures in humidified fuel
gases after Tao and Irvine [274]. YSZ electrolyte thickness was 0.3 mm.
4426
shows the performance of a cell with (La0.75 Sr0.25 )0.9 - • No reactivity with the electrolyte during fabri-
Cr0.5 Mn0.5 O3 anode and LSM cathode measured at dif- cation process. This is particularly important if
ferent temperatures. The maximum power density was the cell structure is formed by co-sintering. As
0.47 W cm−2 at 900◦ C, which is considered to be com- most of electrolyte materials require high sin-
patible to the cell based on Ni/YSZ cermet anodes, con- tering temperature (1300 to 1500◦ C), the reac-
sidering that the YSZ electrolyte used in the cell had a tivity and interface reaction between the elec-
thickness of 0.3 mm. trode support and electrolyte should be none or
Mixed ionic and electronic conducting ox- minimum.
ides such as SrFeCo3 Ox , SrCo0.8 Fe0.2 O3 and • High strength of the electrode support structure.
La0.6 Sr0.4 Fe0.8 Co0.2 O3 (LSCF) were investigated for Cell strength is determined by the strength of the
their electrochemical activity for the oxidation of electrode support structure. Sufficient cell strength
H2 and CH4 fuels [275, 276]. Different to their high is needed for easy handling during the cell fab-
electrocatalytic activity for the O2 reduction reactions rication and stacking. Also, cell should be strong
[277], the oxide anodes showed poor electrochemical enough to withstand the thermal and mechanical
activity for the oxidation reactions of both H2 and CH4 . stress during operation.
It is well known that LSCF materials without protective • High permeability for the fuel gas and the reaction
layer decompose readily and are not stable in exposing products H2 O and CO2 . As the electrode support
to reducing atmosphere [278]. Other conducting oxides structure is usually in the thickness of 500 to 2000
studied as potential anode materials include cubic µm, polarization losses due to gas diffusion can be
perovskite Sr2 GaNbO6 [279], tetragonal tungsten significant.
bronze type A0.6 Bx Nb1−x O3 (A = Ba, Sr, Ca, La and • Good sintering compatibility. Sintering behavior
B = Ni, Mg, Mn, Fe, Cr, In, Sn) [280], nonstoichio- of the electrode support and electrolyte must be
metric mixed perovskites such as SrCu0.4 Nb0.6 O2.9 , closely matched to reduce the bending and warping
SrMn0.5 Nb0.5 O3−δ or Sr2 Mn0.8 Nb1.2 O6 [281, 282], and to increase the production rates.
and pyrochlore Gd2 (Ti1−x Mox )2 O7 [283]. Table I sum- • High electrical conductivity to reduce the ohmic
marizes the electrical and electrochemical properties loss of the cell and high thermal conductivity to
of some conducting oxide studied as potential anode respond quickly to temperature swing in the cell
materials. Large effort is still needed to understand and stack.
the conductivity and electrochemical behaviour of • Good microstructure, surface and shrinkage prop-
conducting oxides under fuel environment and to erties for easy deposition and densification of thin
improve significantly the electrocatalytic activity electrolyte layers.
and stability for the oxidation reaction of H2 and • Finally the cost of the material and automation of
hydrocarbon fuels such as CH4 under SOFC operating the processing needs to be considered.
conditions.
Ni/YSZ based electrode materials satisfy most of the
considerations for YSZ based electrolyte cells. Ni/YSZ
6. Development of anode-supported cermets are highly electrically and thermally conduc-
structures tive. Ni/YSZ cermet anodes can be fired with YSZ
It is increasingly clear that for the development of com- electrolyte up to 1400◦ C for the densification of the
mercially viable SOFC technologies, a reduction of electrolyte with little reactivity between Ni and YSZ
the operating temperature from traditionally 1000◦ C electrolyte. With cathode-supported structure such as
to the range of 600 to 800◦ C is essential. Low operat- Sr-doped LaMnO3 , the forming temperature would
ing temperature not only widens the selection of ma- have to be 1300◦ C or lower in order to avoid the
terials for the electrode, electrolyte, interconnect and formation of resistive La2 Zr2 O7 phase at the elec-
manifold components of SOFC but also significantly trode/electrolyte interface [284–287]. Thus, sintering
reduces the risk of thermal shock and interface reac- YSZ thin film on LaMnO3 -based oxide substrate is ex-
tivity between various cell components and thus in- pected to be more difficult than sintering on a Ni/YSZ
creases the cell performance stability and reliability. cermet anode substrate. Gas diffusion limitation is also
However, lower operating temperature requires high a less problem on the anode side as compared to that
electrode electrocatalytic activity and high ionic con- on the cathode side. At 800◦ C the molecular diffusion
ductivity of electrolyte to compensate the cell loss with- coefficient of H2 /H2 O system is ∼8.4 cm2 s−1 , which is
out penalty for the power density achieved at high tem- considerably higher than ∼2 cm2 s−1 of O2 /N2 system.
peratures. There are two different ways to achieve this The effective binary diffusion coefficients of H2 /H2 O
objective: one is the development of electrolyte with are also considerably higher than those of O2 /N2 under
much higher ionic conductivity than YSZ and the sec- SOFC operating conditions [288]. Porous structure and
ond is to reduce the thickness of YSZ electrolyte using porosity of the anode substrates can be controlled by
electrode supported structures. Electrode supported cell anode composition and addition of pore formers such as
structure is commonly used to reduce the electrolyte rice and corn starch, carbon black and graphite [289].
thickness. Primdahl et al. [290] reported that additing 40 vol%
The choice of materials for the electrode supported corn starch as pore-former to the anode substrates could
structure is primarily related to a number of important reduce the electrode polarization resistance from 0.15
considerations; to 0.08 cm2 at 850◦ C. The cost of Ni/YSZ materials
4427
T A B L E I Conductivity and electrochemical properties of selected conducting oxides studied as potential anode materials. Electrode polarization
resistance (RE ) was measured at open circuit by electrochemical impedance spectroscopy
σ /S cm−1 RE /cm2
a Re indicates reducing conditions in H2 (e.g., 5%H2 /95%Ar or PO2 is ≤10−20 ) and Ox indicates oxidizing conditions in air.
bH and CH4 usually indicates moist H2 and CH4 with 3% H2 O.
2
can be reduced by using TiO2 or Al2 O3 as cost effective In the last few years, Ni/doped-ceria cermets have
alternatives to YSZ in the anode supported structure been increasingly studied as the supports for the IT-
[291]. SOFC based on high conductivity electrolyte materi-
The state-of-the-art anode-supported planar SOFC als such as doped-ceria [296–298]. Various fabrica-
is based on Ni/YSZ cermet as the support [292–295]. tion techniques have been explored and investigated
4428
in the fabrication of porous anode support substrates. on Ni/YSZ substrates usually tends to warp towards
The most common one is probably the tape casting the anode layer during sintering. Alumina is a sintering
technique. inhibitor and also has a relatively low thermal expan-
Tape casting is an established industrial process to sion coefficient (TEC), which can bring the TEC of
make large and flat ceramic tapes, plates and lami- the anode substrate close to that of YSZ. Thus, addi-
nated ceramic structure, and thus is suitable for making tion of alumina in the Ni/YSZ structure can signifi-
anode-supported planar solid oxide fuel cell structure. cantly improve the flatness of the substrate [289]. On
Tape casting involves spreading of ceramic powders the other hand, Müller et al. [304] showed that by cofir-
and organic ingredients onto a flat surface where sol- ing screenprinted Ni/YSZ cermet anode and YSZ elec-
vents are allowed to evaporate. After drying, the result- trolyte green tape, anode polarization losses were re-
ing tape develops a leather-like consistency and can be duced due to the improved contact between the YSZ
stripped off from the casting surface. Typically, tape phase in the cermet and YSZ electrolyte. The mis-
cast anode layer from 1 to 2 mm thick and tape cast match between the anode and YSZ and thus the me-
electrolyte layer from 40 to 100 µm thick are produced chanical stresses in the Ni/YSZ cermet anode layer and
and these two tapes are laminated and after rolling or YSZ substrate can be reduced by changing the anode
calendering, the green laminates are cut to size and coating from a continuous geometry to a large num-
sintered at 1400◦ C in a specially designed kiln fur- ber of small sized individual areas [305]. The best re-
nace to ensure the parts are all flat. The final anode- sults of the patterned anode layer were observed on the
supported structures are produced with anode thickness honey-comb design with low curvature and stress. To
of 500–1000 µm and electrolyte thickness of 15–40 overcome the sintering profile mismatch, anode sub-
µm. Fig. 22 shows typical structure of Ni/YSZ cer- strate tape can also be heated to produce a presin-
met anode-supported thin YSZ electrolyte cell as com- tered body strong enough to be handled for electrolyte
pared to electrolyte supported cell structure. With tape- deposition.
calendering process, the YSZ electrolyte thickness can Will et al. [306] gave a detailed review on the tech-
be reduced to 5–10 µm [299–301]. However, shrink- niques in the deposition and preparation of thin and
age of anode and YSZ electrolyte materials can be very dense electrolyte layer on porous anode substrates.
different [54, 302]. Mismatch in densification of such This includes vacuum slip casting [307], magnetron
bilayer structure will cause intolerable bending and/or sputtering [308], spray and spray pyrolysis [309, 310],
cracking of the structure during co-firing [291, 303]. screen printing [297], electrophoretic deposition [311–
Thus, sintering of the laminated anode and electrolyte 313] and other thin film deposition techniques. For
tapes is critical in producing flat anode-supported struc- small cells and laboratory investigation purpose, anode-
ture as the sintering profiles of the anode and electrolyte supported structures were often produced by powder
tapes are very different. Fig. 23 shows the shrinkage compacting and die-pressing [297, 309, 314, 315].
profile of Ni/8YSZ cermet tapes and 8YSZ electrolyte Dense electrolyte film as thin as 8 µm was prepared on
tape as function of sintering temperature. Both carbon porous substrates by dry-pressing process [316]. Yoo
content and type of 8YSZ powder have significant ef- et al. [317] used compacting and drying of Ni/YSZ
fect on the shrinkage process of Ni/8YSZ cermet tapes slurry to make 50 × 50 mm size anode substrates.
and 8YSZ electrolyte tapes. The bilayer structure based Anode-supported cells with diameter of 120 mm were
Figure 22 Typical structure of (a) YSZ electrolyte-supported cell and (b) Ni/YSZ cermet anode-supported thin YSZ electrolyte cell prepared by tape
casting.
4429
surface resulted in open pores on the YSZ electrolyte
films deposited (Fig. 24b and c). Thus the pore di-
ameter of the substrate surface needs to be in the or-
der of the grain size of the deposited film to achieve
dense and uniform YSZ electrolyte film (Fig. 24d and
e). This can be done by using an interlayer or func-
tional layer with finer microstructure and low poros-
ity [282]. The function layer is also used to promote
the electrode reaction at the electrode/electrolyte inter-
face. Hobein et al. [324] shown that the surface arte-
facts of the function layer should be smaller than the
film thickness in order to avoid the defects on the YSZ
film deposited by pulse laser deposition technique. The
porous structure of the surface of the function layer
can be changed by high temperature annealing [325].
The porosity of both anode substrate and functional
Figure 23 Shrinkage profile of Ni/8YSZ cermet tape with addition of layer decreased with increasing annealing temperature
various carbon contents (empty symbols) and 8YSZ tape (filled symbols) and annealing at 1380–1400◦ C created a dense func-
as function of sintering temperature. tion layer surface for the deposition of gas-tight YSZ
electrolyte film. Kek et al. [326] found that the ionic
conductivity of deposited YSZ film on Ni/YSZ sup-
also sucessfully fabricated by die-pressing technique port varied with the sintering temperature of the anode
[318]. Song et al. [319] reported the fabrication and substrate, but no explaration was given. The structure
performace of anode-supported tubular cell using ex- and stability of the Ni/YSZ cermet substrates are im-
trusion technique. Power density in the range of 570 portant to the deposition and properties of YSZ thin
to 800 mW cm−2 at 750◦ C was reported for prototype electrolyte. Cassidy et al. [327] studied the effect of
anode-supported cells based on tape casting technique the volume change of NiO to Ni in the cermet sub-
with Ni/YSZ cermet anode and LSM cathode [293, strates on the stability of YSZ electrolyte. The initial
307]. Power output as high as 2 W cm−2 at 1000◦ C reduction seems to have a little effect on the stability
has been reported on Ni/YSZ anode supported cells of YSZ thin electrolyte but the reoxidation of Ni to
[320, 321]. NiO in the cermet support led to the crack of the YSZ
Simwonis et al. [322] reported coat-mix (CM) pro- electrolyte.
cess for the production of porous Ni/YSZ cermet sub- Preparation and physical properties of Ni/TiO2 cer-
strates. The powder produced by CM process was char- mets were investigated for the anode support for pla-
acterized by tiny rigid agglomerates and the substrates nar SOFC [328]. A thin Ni/YSZ interlayer or func-
were prepared by pressing the powder in a die at 120◦ C. tion layer was used for the electrochemical reaction
The green plates can be prepared up to the dimensions at the anode/electrolyte interface. In addition to the
of 330 × 330 × 2.7 mm. After pre-sintering at 1200◦ C cost saving as compared to Ni/YSZ substrates, Ni/TiO2
the porous substrate was coated with a functional layer substrates have thermal expansion coefficient closer
of Ni and 8YSZ via vacuum slip casting [282]. Elec- to that of YSZ electrolyte and the electrical conduc-
trolyte with thickness of 5–10 µm was deposited by tivity is compatible with that of Ni/8YSZ substrates.
the same technique, followed by sintering at 1400◦ C. Softening of the Ni/TiO2 cermet at temperatures above
The substrates prepared by CM process were shown 800◦ C is also beneficial for the release of stresses in-
to have higher gas permeability, better pore size dis- troduced during stack manufacturing [329]. Yan et al.
tribution and pore structure as compared to Ni/8YSZ [330] studied the electrical and microstructural prop-
substrates prepared by tape casting [323]. However, erties of Ni/La0.9 Sr0.1 Ga0.8 Mg0.2 O3 (Ni/LSGM) anode
automation of CM process may be of concern. Vari- substrates. The electrical conductivity increased with
ous pore-former can be added to the anode substrates the Ni content. However, the electrical conductivity ap-
to improve the porous structure and to improve the cell pears to be low. For example, the electrical conductiv-
performance. ity of Ni (60%)/LSGM (40%) cermet anode was ∼45
Surface morphology of the substrate such as pore S cm−1 at 800◦ C. Among the compositions studied, the
size and pore size distribution is critical for the depo- substrates with 60% Ni content were considered to have
sition of thin and high dense electrolyte film on the the best microstructure for the deposition of LSGM thin
Ni/YSZ anode substrates as the morphology of the de- elecrlyte. To avoid the interaction between LSGM and
posited film follows that of the substrate surface. Fig. 24 Ni in the substrate, a SDC interlayer with a thickness of
shows the morphology of the YSZ film deposited on 2–5 µm was used. Yan et al. [331] also proposed a novel
YSZ and Ni/YSZ cermet substrate by magnetron sput- method to prepare Ni/YSZ anode supported LSGM
tering. Thin YSZ film deposited has the same grain electrolyte thin film cell. In this method, thin LSGM
and grain boundary pattern as that of the YSZ sub- electrolyte film was deposited onto the surface of a
strate (Fig. 24a), indicating that the surface morphol- porous YSZ substrate, sintered and followed by impreg-
ogy of the YSZ thin film follows closely the morphol- nation of Ni into the porous YSZ substrate to turn it into
ogy of the substrate. The large pores on the substrate electrically conducting Ni/YSZ cermet substrate. The
4430
Figure 24 Morphology of the YSZ film deposited on YSZ and Ni/YSZ cermet anode substrate by magnetron sputtering. (a) YSZ film deposited
on YSZ substrate, (b) and (c) YSZ film deposited on Ni/YSZ cermet substrate, showing that the defects in the YSZ electrolyte film is due to the
large pores on the anode substrate surface, and (d) and (e) dense and uniform YSZ film deposited on Ni/YSZ anode substrate with optimized surface
morphology.
maximum power of 0.85 Wcm−2 was achieved at 800◦ C There was a significant increase in porosity of the re-
with H2 /air. oxidized sample as compared to the as-sintered sample.
Another important property of anode supported elec- The reduction process of NiO in NiO/YSZ cermets is
trolyte structure is the structure stability and perfor- also not a simple one. Mori et al. [334] studied the
mance recoverability during reduction-oxidation cy- interaction between NiO and YSZ by TPR and identi-
cle (or RedOx cycle) either due to accidental system fied five different states of NiO species in the NiO/YSZ
shut-down or system service requirement. Due to the system. In this respect, porous metallic alloy substrates
electrochemical and mechanical requirements of the may be attractive alternatives as electrode-supported
anode supported electrolyte structure, the cell should structure [335–339]. Different kinds of metallic sub-
be able to withstand a significant number (>5/year) of strates such as Ni and FeCr alloy were used including
RedOx cycles without significant degradation of the felt, foams, nets and porous sintered plates. Ni/YSZ
performance [332]. To understand the RedOx behav- anode, YSZ electrolyte and LSM cathode components
ior of Ni/YSZ cermet materials, Tikekar et al. [333] were deposited onto porous metallic substrate by a vac-
studied the kinetics of reduction and re-oxidation of uum plasma spray process [335–337] or by conven-
dense Ni/YSZ cermets at temperature range of 650– tional ceramic processing techniques such as screen-
800◦ C. The reduction process is interface controlled, printing and dip-coating [338, 339]. Cell performance
while the re-oxidation kinetics is diffusion controlled. of 280 mW cm−2 at 0.7 V and 800◦ C was achieved in
4431
H2 /air with YSZ electrolyte and the power density in- tive and stable alternative anodes for the hydrocarbon
creased to 430 mW cm−2 with the scandia-stabilized fuels.
zirconia electrolyte [340]. The advantages of metallic Stability of microstruture and interface at elec-
substrate-supported cells include low cost, high me- trode/electrolyte region is an important issue in the de-
chanical strength and the ability in withstanding the velopment of SOFC technologies. However, stability
rapid thermal cycling. of individual components in SOFC is not only related
to the component itself but also the interfacial reac-
tions between various components of a SOFC stack.
7. General comments For example, in the case of SOFC based on metallic in-
Ni/YSZ based cermet materials are still the most terconnect, the interaction between chromium gaseous
common anodes in SOFC due to their high electro- species such as CrO2 (OH)2 and the cathode materials
chemical activity for H2 oxidation reaction and demon- such as LSM and LSCF can cause significant degrada-
strated long-term stability at SOFC operating condi- tion of the electrocatalytic activities for the O2 reduction
tions. Fabrication and microstructure of the Ni/YSZ reactions on LSM materials [342–344]. As compared
cermet materials have been extensively studied and to the serious poisoning effect of chromium species
significant understanding and knowledge of the com- on the degradation of the polarization performance on
plex inter-relations between the material properties, the LSM cathodes, the effect of metallic interconnect
microstructure, electrochemical process and the fab- on the polarization performance of Ni/YSZ cermet an-
rication process parameters have been achieved. The odes is generally much smaller [345]. Ni/YSZ cermet
electrochemical performance of Ni/YSZ cermet anodes anodes are also very stable with YSZ electrolyte and
for H2 and CH4 oxidation reactions can be further im- there are basically no chemical reactions between Ni
proved by replacing YSZ with mixed ionic and elec- and YSZ at the temperature range of the fabrication
tronic conductors (MIEC) such as doped ceria or by and fuel cell operation [110]. However, NiO is slightly
impregnation or doping of noble metal or MIEC ox- soluble in YSZ with solubility limit of ∼2% NiO in
ide catalyst. Nevertheless, the long-term stability of YSZ after heating at 1400◦ C for 12 h in air [346]. Sim-
such modified cermet anodes has not yet been fully ilar results were also reported for the NiO/YSZ system
demonstrated. sintered at 1600◦ C for 80 h [347]. Linderoth et al. [348]
R&D activities in the development of modified Ni- investigated the effect of NiO and NiO-to-Ni transfor-
based and/or Ni-free materials for oxidation (or con- mation on the conductivity of YSZ. The presence of
version) reactions of hydrocarbon fuels (e.g., methane) NiO reduced the conductivity of 8YSZ by as much as
in SOFC are increasing significantly since the last 20% in air. Transformation of NiO to Ni under reduc-
decade. However, there are significant discrepancies ing conditions can cause the cubic to tetragonal phase
in the results on the electrical properties and perfor- transformation in YSZ, resulting in further reduction in
mance of the Ni-based or Ni-free anodes for oxida- conductivity. On the other hand, impurities such as Si in
tion reactions of methane under SOFC operation en- the electrode and YSZ electrolyte can have significant
vironment, as highlighted recently by Mogensen and effect on the electrode behavior of Ni anodes [349, 350].
Kammer [341]. Steele [40] suggested that anode ma- Nevertheless, the effect of dissolved Ni in YSZ and im-
terials for the electrochemical oxidation of hydrocar- purity segregation at the electrode/electrolyte interface
bon fuels such as CH4 should have good electronic in the case of Ni/YSZ cermet anode on the electrolyte
conductivity of 100 S cm−1 , high oxygen surface ex- stability, electrode behavior and long-term performance
change kinetics, high activity for oxidation of hydro- stability is still not clearly understood.
carbon fuels and stability in reducing environment. One of the major obstacles in the commercial intro-
From the oxide materials reviewed, there is hardly a duction of SOFC system is the high cost as compared
material reported so far that satisfies all the require- to entrenched power generation technologies. As SOFC
ments for anodes for direct electrochemical oxidation stack is the only one component of the SOFC system,
of hydrocarbon fuels. Low electronic conductivity of the stack cost should only be a fraction of the system
the anode coatings based on doped ceria, titanate- and cost, which has been targeted to be ∼US$400/kW by the
chromite-based oxides will pose a serious challenge US Department of Energy’s Solid State Energy Conver-
in the current collector design and probably limit the sion Alliance (SECA) program [351]. Such aggressive
practical application of the materials as anodes. The cost reduction would preclude the use of expensive or
low electrical conductivity of ceria-based anodes is par- exotic raw materials and complex processing processes
tially compensated by using metal paste current collec- for anode and anode substrates. It has been recognized
tor such as Au [225]. In reality such approach may that the fabrication and assembly methods employed in
not be economically and technically viable. In addi- the construction of fuel cell stacks are a significant stack
tion to the generally low and, in some cases, unsta- cost element. It is important to select a manufacturing
ble conductivity behavior, the overall electrochemical process that is not only cost competitive but also pro-
activity of the chromite and titanate based perovskite vides a means for stack performance improvement. Re-
anodes is poor as compared to that of conventional ducing the fabrication steps would significantly reduce
Ni/YSZ based cermet anodes. The development of Ni- the production cost. As shown by Rietveld et al. [294],
free alternative materials based on various conduct- tape casting steps for fabrication of anode substrates can
ing oxides is largely in the laboratory stage and there be reduced from original three steps to one by adjust-
are significant challenges in the development of effec- ing the suspension. Omitting the pre-sintering step for
4432
the anode substrate also improved screenprinting yield to accurately separate the electrode polarization in order
from less than 40 to 95% due to the easier handling to understand the electrode behavior of anode substrate
ability of the tapes. Basu et al. [352] shows that by us- for the fuel oxidation and/or internal reforming reac-
ing wet powder spraying instead of vacuum slip casting tions. As the microstructure requirement of thick anode
to deposit the anode function layer, one firing step can substrates is fundamentally different from that of thin
be omitted with no effect on the cell performance. Co- screenprinted anode coating, it is expected that elec-
firing process is suitable for mass production and to pro- trode behavior of the thick electrode substrates would
duce anode-supported thin electrolyte cells, reducing be significantly different too [374, 375].
material and fabrication cost [353, 354]. However, not
all electrode and electrolyte systems are feasible with References
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ics of anodic reactions are primarily concentrated on 6. T . K A W A D A and H . Y O K O K A W A , in “Key Engineering
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