Академический Документы
Профессиональный Документы
Культура Документы
www.elsevier.nl/locate/electacta
Abstract
Solid oxide fuel cells (SOFCs) are advanced electrochemical reactors operating at a high temperature. SOFCs are
presently under development for a variety of electric power generation applications with high energy conversion
efficiency. This paper reviews the science and technology of SOFCs with emphasis on discussion of their component
materials. © 2000 Elsevier Science Ltd. All rights reserved.
1. Introduction the phosphoric acid fuel cell (PAFC), the molten car-
bonate fuel cell (MCFC), and the solid oxide fuel cell
The origin of fuel cells goes back to the middle of the (SOFC) have been mainly developed. These fuel cells
last century, their principle was first described by Sir are characterized by the electrolyte used, which in turn
William Grove in 1839 [1]. His fuel cell, operating at determines the operating temperature. The characteris-
room temperature, used a dilute sulfuric acid elec- tics and the current status of different types of fuel cells
trolyte, a hydrogen anode and an oxygen cathode. At are summarized in Table 1. The most advanced fuel cell
system is the PAFC. More than 200 PAFC units have
that time no conventional batteries such as lead acid
been introduced as on-site electric power plants. How-
batteries or Leclanche type cells were yet available and
ever, a serious problem for commercialization of PAFC
so four fuel cells were connected in series and were
is their high unit cost. PEFCs have recently attracted
applied to the electrolysis of water. Thus, fuel cells
significant attention as a potential source of primary
become the first electric high power supply.
power in transportation applications. As shown in
Fuel cells are energy conversion devices that produce
Table 1, SOFCs have exceptional potential for use as
electricity directly from a gaseous fuel by electrochemi-
electric power generation systems, because of their high
cal combination of the fuel with an oxidant. Fuel cells
energy conversion efficiency which can reach up to
have many advantages compared to conventional elec-
65%. In addition, SOFCs have many advantages such
tric power generation systems, such as high conversion as multi-fuel capability and simplicity of system design
efficiency, which is relatively independent of size, as [2]. Furthermore, the exhaust heat can be used as a heat
well as environmental compatibility. The first successful source for a variety of processes. This together with the
practical applications of fuel cells was for space appli- possibility of utilizing the remaining energy in a bot-
cations in the 1960s. After further R&D efforts in the toming cycle for electric power generation leads to a
1980s and 1990s, fuel cells have recently attracted new further increase in the overall efficiency. The pressur-
attention due to their potential for use in stationary and ized SOFC can be used to replace combustors in gas
distributed electric power stations as well as in trans- and steam turbines. Such integrated SOFC-combustion
portation applications. At this stage, four types of fuel turbine power systems are expected to reach efficiencies
cells, namely, the polymer electrolyte fuel cell (PEFC), approaching 70% [3]. The high efficiency will contribute
to reduce CO2 emissions. In this review, science and
E-mail address: yamamoto@chem.mie-u.ac.jp (O. Ya- technology of SOFCs as well as their future prospects
mamoto) will be discussed.
0013-4686/00/$ - see front matter © 2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 1 3 - 4 6 8 6 ( 0 0 ) 0 0 3 3 0 - 3
2424 O. Yamamoto / Electrochimica Acta 45 (2000) 2423–2435
Table 1
The characteristics and current status of the different types of fuel cell
a
Allied signal.
b
Fuji electric.
c
MCFC Research Association, Japan.
d
Siemens Westinghouse.
e
Mitsubishi Heavy Industry and Electric Power Development, Japan (at 5 atm).
2. Principle and histrical background of SOFC is still used as the electrolyte. The oxide ion conductiv-
ity of YSZ is around 0.1 S/cm at 1000°C. Together with
The operating principle of a SOFC with an oxide ion the electrolyte, the other SOFCs components have been
conductor is schematically shown in Fig. 1. When an studied for many years, but due to the high operating
external load is applied to the cell, oxygen is reduced at temperature, the choice of materials remains limited. In
the porous air electrode to produce oxide ions. These Baur and Preis’ first SOFC, iron or carbon were used as
ions migrate through the solid electrolyte to the fuel the anode while Weissbart and Ruka [6] of Westing-
electrode, and they react with the fuel, H2 or CO, to house Electric (now Siemens Westinghouse Power,
produce H2O or CO2. Alternatively, a proton conduct- SWH) in 1962 used platinum. At present nickel is the
ing solid electrolyte can be used, where H2 is oxidized most commonly used material because of its high cata-
to produce protons that subsequently react with oxygen lytic activity and low cost. The nickel-YSZ cermet
to form water. In some cases, CH4 can be oxidized anode can operate at a temperature as low as 500°C.
directly on the anode to form CO2 and H2O. The
The cathode materials must be stable in the oxidizing
open-circuit voltage, Eo, of the cell can be calculated
environment, have good electronic conductivity and
from the free energy change, DG, of the electrochemical
sufficient catalytic activity for oxygen reduction under
reaction or from the partial pressure of the oxygen
operating conditions. Many types of cathode materials
Po(c) at the cathode and Po(a) at the anode:
have been examined. Baur and Preis used Fe3O4 as the
Eo = −DG/nF= (RT/nF) ln Po(c)/Po(a) (1) cathode. The electrical conductivity of Fe3O4 is as high
as 3 × 102 S/cm at room temperature, but its catalytic
In this equation, R is the gas constant, T the absolute activity is insufficient. Weissbart and Ruka [6] used
temperature, F the Faraday constant, and n the electron
platinum as the cathode. At 1011°C, the cell voltage,
equivalent of oxygen (n=4). The cell voltage at 1000°C
is about 1 V for the SOFC with pure hydrogen and air.
The cell voltage drops as current is drained due to
polarization. The total polarization of a cell, h, is the
sum of three terms: anode polarization, ha, cathode
polarization, hc, and resistance polarization, hr.
materials and fabrication processes. A modified design terials for low temperature SOFCs were available. A
of the monolithic configuration has been developed by lower operating temperature in the range of 500 – 800°C
Chubu Electric Power Co and Mitsubushi Heavy In- would have many advantages. Costly lanthanum
dustry, and was named the Mono Block Layer Built chromite interconnects could be replaced by a conven-
(MOLB). A 5-kW scale MOLB type SOFC was built tional metallic interconnect, and the selection of gas
and successful results were obtained [14]. seal materials in planar SOFCs would be easier. SOFCs
Up to the present, large scale SOFC units have been operating at 500°C or lower are being considered for
operated at around 1000°C because no acceptable ma- applications in electric vehicles [15].
the operating temperature. Bismuth oxide systems show the highest conductivity. These systems, however, ex-
hibit high electronic conductivity under reducing atmo-
sphere, because of the reduction of Bi3 + to Bi2 + [23].
The most promising traditional materials for low tem-
perature operation of SOFCs are CeO2 doped with an
alkaline earth or rare earth oxide. The conductivity of
Ce0.8Gd0.2O1.9 [24] is 1.2×10 − 2 S/cm at 800°C and
3.7× 10 − 3 S/cm at 600°C. At higher oxygen partial
pressures the material is reported to have a purely ionic
conductivity. At lower oxygen partial pressures, as pre-
vail at the anode side of the SOFC, CeO2 becomes
partially reduced [25]. This leads to predominantly elec-
tronic conductivity in a large volume fraction of the
electrolyte extending from the anode side. In Fig. 9,
total electrical conductivities of Ce0.8Sm0.2O1.9 are
shown as a function of oxygen partial pressure [26]. The
increasing conductivity at lower oxygen partial pressure
is due to the contribution of the electronic conductivity.
At high oxygen partial pressure, the total electrical
conductivity is predominantly ionic, whereas at low
oxygen partial pressure it is predominantly electronic.
The efficiency of SOFCs with the mixed ionic-electronic
conductors of the CeO2 based oxide depends on the
Fig. 8. Temperature dependence of electrical conductivity for operating temperature and the thickness of the elec-
oxide ion conductors (lower temperature range). trolyte due to the partial reduction of the electrolyte.
Godlickemeier and Gauckler [26] analyzed the effi-
ciency of cells with ceria-based electrolytes by consider-
ing electrode overpotentials. The maximum efficiency of
these cells was 50% at 800°C, 57% at 700°C, and 60% at
600°C. In practical operation, it is also necessary to
consider the fuel efficiency. Generally, the fuel effi-
ciency is less than 80%. Therefore, SOFCs with the
CeO2 based electrolytes should be operated at tempera-
tures lower than 600°C in order to obtain a total
efficiency exceeding 50%. A SOFC based on
Ce0.8Gd0.2O1.9 at 500°C was examined by Doshi et al.
[17] Using a multilayer tape-casting technique these
authors fabricated an anode supported electrolyte bi-
Fig. 9. Total electrical conductivity of Ce0.8Sm0.2O1.9 − x at layer with an electrolyte thickness of 30 mm and anode
600, 700, and 800°C as a function of oxygen partial pressure. thickness of : 250 mm. Fig. 10 shows the performance
at 500°C of a cell with the NiCe0.8Gd0.2O1.9 cermet
anode and a cathode developed by Argonne National
Laboratory. The total cell resistance, including elec-
trode polarization for both electrodes, was 1.3 V cm2,
0.7 V cm2 resulting from the electrolyte, 0.6 V cm2 from
the cathode, while the loss from the anode was negligi-
ble. A cell voltage of 0.7 V was obtained at 150
mA/cm2 and the maximum power density was 140
mW/cm2. Another approach for the ceria based elec-
trolyte is to use a bi-layer electrolyte with YSZ. Tsai et
al. [27] developed an electrolyte consisting of a 4 – 8 mm
thick Y2O3 doped ceria layer with a 1 – 1.5 mm thick
Y2O3 doped zirconia layer on the fuel side. The thin
Fig. 10. Performance of SOFC with anode-supported bi-layer electrolyte provided a near theoretical open
Ce0.8Gd0.2 electrolyte and La0.8Sr0.2Fe0.8Co0.2O3 − cathode at circuit voltage and the electrolyte resistance was 0.25 W
–
500°C. cm2 at 600°C and 0.45 V cm2 at 550°C.
2430 O. Yamamoto / Electrochimica Acta 45 (2000) 2423–2435
Table 3
Electrical and mechanical properties of zirconia based oxidesa
Materials Conductivity (S/cm) Bending strength (MPa) Thermal expansion coefficient (10−8/K)
1000°C 800°C
a
3YTZP: 3 m/o Y2O3ZrO2, 3YbTZP: 3 m/o Yb2O3ZrO2, 2.9SSZ: 2.9 m/o Sc2O3ZrO2, 11SSZ1A:(11 m/o Sc2O3ZrO2)-1 w/o
Al2O3, 11SSZ20A: (11m/oSc2O3ZrO2)-20 w/o Al2O3.
Takeda et al. [37] studied the electrical conductivity and More recently, Uchida et al. [43] reported an interest-
the catalytic activity for oxygen reduction of perovskite ing result concerning hydrogen oxidation on an active
oxide electrodes, La1 − x Srx MO3(MCr, Mn, Fe, Co). hydrogen electrode. The IR-free polarization of the
The cathodic polarization curves at 800oC for sputtered active anode attached to different types of zirconia
La1 − x Srx MO3 on YSZ are shown in Fig. 12. The electrolytes was greatly influenced by the conductivity
La1 − x Srx CoO3 electrode has high catalytic activity for of the zirconia used. The doped zirconia with higher
oxygen reduction. The conductivity measurements also ionic conductivity exhibited a higher exchange current
showed that the cobalt system had the highest conduc- density for the hydrogen electrode at 800 – 1000°C as
tivity in these perovskite systems, but the compatibility shown in Fig. 13, where Sm doped CeO2 with Ru was
with YSZ was less good. The thermal expansion coeffi- used as the anode catalyst. The results indicate that the
cient of LaCoO3 is :22–24×10 − 6/K and that of reaction rate of H2 oxidation was controlled by the
YSZ : 10–11 ×10 − 6/K. La1 − x Srx CoO3 reacts readily
with YSZ forming the low conductivity products,
La2Zr2O3 and SrZrO3 [38]. No reaction product has
been observed when coupling doped CeO2 and La1 −
xSrx CoO3. For this reason, the La1 − x Srx CoO3 systems
have been used together with CeO2 based electrolytes in
SOFCs at low operating temperatures. However, the
mismatch in thermal expansion between CeO2 and
La1 − x Srx CoO needs to be improved.
More recently, La1 − x Srx Fe1 − yCoyO3(LSFC) has
been examined extensively for SOFCs operating below
900°C [39]. This system showed a good electrical con-
ductivity at temperatures between 600 and 800°C, high
oxygen surface exchange coefficient and high oxygen
self diffusion coefficient. The oxygen self diffusion co-
efficient (D*) of LSFC at 500°C of 2.6 ×10 − 9 cm2/s
compared to that of La0.8Sr0.2MnO3 at 10 − 12 cm2/s at
1000°C [40]. The LSFC /Ce0.9Sm0.1O1.95 combination
exhibits fast electrode kinetics. LSFC does not react
with ceria-based electrolytes and has a compatible ther-
mal expansion coefficient [41]. Excellent behavior of the
cell Ni-YSZ/Ce0.8Gd0.2 O1.9/LSFC has been proved by
Berkel et al. of ECN [42]. A cell voltage of 0.7 V was
obtained at 150 mA/cm2 and 603°C with a self-sup- Fig. 12. Cathodic polarization curves at 800°C for a sputtered
ported 0.1–0.25 mm thick Ce0.8Gd0.2O1.9 electrolyte. La1 − x Srx MO3 film.
2432 O. Yamamoto / Electrochimica Acta 45 (2000) 2423–2435
Table 4
Stack performance of large scale SOFCa
a
SWH: Siemens Whestinghouse Power Co., MHI: Mitsubishi Heavy Industries, EPDC: Electric Power Development Co.,
CEPCO: Chubu Electric Power Co., he: energy conversion efficiency.
O. Yamamoto / Electrochimica Acta 45 (2000) 2423–2435 2433
[6] J. Weissbart, R. Ruka, J. Electrochem. Soc. 109 (1962) [30] M. Feng, J.B. Goodenough, Eur. J. Solid State Inorg.
723. Chem. 31 (1994) 663.
[7] C.S. Tedmon, H.S. Spacil, S.P. Mitoff, J. Electrochem. [31] T. Ishihara, T. Shibayama, M. Honda, H. Furutani, Y.
Soc. 116 (1969) 1170. Takita, in: Abstract of 1998 Fuel Cell Seminar, Palm
[8] W. Wersing, E. Ivers-Tiffee, M. Schiessi, H. Greiner, in: Springs, USA, 1998, p. 104.
O. Yamamoto, M. Dokiya, H. Tagawa (eds), Proceeding [32] K. Huang, M. Feng, J.B. Goodenough, C. Milliken, J.
of the International Symposium on Solid Oxide Fuel Electrochem. Soc. 144 (1997) 3629.
Cells, Nagoya, Japan, 1989, p. 33. [33] J. Wolfenstine, Electrochem. Solid-State Lett. 2 (1999)
[9] S.C.Singhal, in: U. Stimming, S.C. Singhal, H. Tagawa, 210.
W. Lehnert (eds), Proceeding of the fifth International [34] H. Uchida, N. Maeda, H. Iwahara, Solid State Ionics 11
Symposium on Solid Oxide Fuel Cells, 1997, p. 37. (1983) 117.
[10] F.J. Rohr, in: P. Hagnemuller, W. van Gool (Eds.), Solid [35] Y. Mizutani, M. Tamura, M. Kawai, K. Nomura, Y.
Electrolytes, Academic Press, New York, 1978, p. 431. Nakamura, O. Yamamaoto, in: M. Dokiya, O. Ya-
mamoto, H. Tagawa, S.C. Singhal (eds), Proceedings of
[11] A.O. Isenberg, W.A. Pabst, E.F. Sverdrup, D.H. Archer,
Fouth Internationa Symposium on Solid State Fuel Cells,
in: Proceedings of the sixth Biennial Fuel Cell Sympo-
Nagoya, Japan, Electrochem. Soc., NJ, USA, 1995, p.
sium, 1969.
301.
[12] Westinghous Electric Corporation, Final Report, Project
[36] E.F. Sverdrup, D.H. Archer, A.D. Glaser, Am. Chem.
Fuel Cell Rep. No. 57, 1970.
Soc. Adv. Chem. Ser. 90 (1969) 301.
[13] J.P. Ackerman, J.E. Young, U.S. Patent No. 4476198,
[37] Y. Takeda, R. Kanno, M. Noda, Y. Tomida, O. Ya-
October 9, 1984.
mamoto, J. Electrochem. Soc. 134 (1987) 2656.
[14] M. Hattri, Y. Esaki, Y. Sakaki, F. Nanjyo, K. Takenobu,
[38] O. Yamamoto, Y. Takeda, R. Kanno, M. Noda, Solid
H.M. Yamoto, in: Ext. Abstract of seventh Symposium
State Ionics 22 (1987) 241.
on Solid Oxide Fuel Cells in Japan, Nagoya, Japan, 1998,
[39] L-W. Tai, M.M. Nasrallah H.U. Anderson, in: S.C. Sing-
p. 19.
hal H. Iwahara (eds), Proceeding of the Third Interna-
[15] R. Doshi, Von L. Richard, J.D. Carter, X. Wang, M.
tional Symposium on Solid Oxide Fuel Cells, Honolulu,
Krumpelt, J. Electrochem. Soc. 146 (1999) 1273.
USA, Electrochem. Soc., NJ, USA, 1993, p. 241.
[16] Y. Arachi, H. Sakai, O. Yamamoto, Y. Takeda, N.
[40] B.C.H. Steele, Solid State Ionics 86/88 (1996) 1223.
Imanishi, Solid State Ionics 121 (1999) 133.
[41] L. Kindermann, D. Dos, H. Nickel, K. Hilpert, C.C.
[17] J.K. Kilner, R.J. Brook, Solid State Ionics 6 (1982) 237.
Appel, F.W. Poulsan, J. Electrochem. Soc. 144 (1997)
[18] A.O. Isenberg, in: J.D.E. Mclntyre, S. Srinvasan, Will 717.
(eds), Proceeding of the Symposium on Electrode Materi- [42] F.P.F. van Berkel, G.M. Christie, F.H. van Heuveln,
als and Processes for Energy Conversion and Storge, J.P.F. Huijsmans, in: M. Dokiya, O. Yamamoto, H.
Philadelphia, USA, Electrochem. Soc., NJ, USA, 1977, Tagawa, S.C. Singhal (eds), Proceedings of Fouth Inter-
p.572. nationa Symposium on Solid State Fuel Cells, Nagoya,
[19] N.Q.Minh, K.Montgomery, in: U. Stimming, S.C. Sing- Japan, Electrochem. Soc., NJ, USA, 1995, p. 1062.
hal, H. Tagawa, W. Lehnert (eds), Proceeding of the fifth [43] H. Uchida, H. Suzuki, M. Watanabe, J. Electrochem.
International Symposium on Solid Oxide Fuel Cells, Soc. 146 (1998) 615.
1997, p153. [44] H. Uchida, M. Yoshida, M. Watanabe, J. Electrcochem.
[20] Y. Mizutani, M. Kawai, K.Nomura, Y.Nakamura, Soc., Submitted.
O.Yamamoto, in: U. Stimming, S.C. Singhal, H. Tagawa, [45] R.J.F. van Gerven, J.H.C. van der Veer, in: Abstracts of
W. Lehnert (eds), Proceeding of the fifth International 1998 Fuel Cell Seminar, Palm Springs, USA, 1998, p. 76.
Symposium on Solid Oxide Fuel Cells, 1997, p196. [46] H. Mori, H. Ohmura, K. Ikeda, K.A. Tomida, in: Ab-
[21] T.H. Estel, S.N. Feng, Chem. Rev. 70 (1970) 339. stracts of Seventh Symposium on Solid Oxide Fuel Cells
[22] O. Yamamoto, Denki Kagaku 63 (1995) 698. in Japan, Tokyo, Japan, 1998, p.27.
[23] T. Takahashi, T. Esaka, H. Iwahara, J. Appl. Elec- [47] H.J. Beie, L.W. Drenckhahn, H. Greiner, B. Rufolf, H.
trochem. 7 (1977) 303. Schichl, in: U. Stimming, S.C. Singhal, H. Tagawa, W.
[24] T. Kudo, H. Obayashi, J. Electrochem. Soc. 122 (1975) Lehnert (eds), Proceeding of the fifth International Sym-
142. posium on Solid Oxide Fuel Cells, 1997, p. 51.
[25] H.L. Tuller, A.S. Nowick, J. Electrochem. Soc. 126 (1979) [48] Y. Sakaki, Y. Esaki, M. Hattori, H. Miyamoto, T. Sa-
209. take, F. Nanjo, T. Matudaira, K. Takenobu, in: U.
[26] M. Godlickemeier, L.J. Gauckler, J. Electrochem. Soc. Stimming, S.C. Singhal, H. Tagawa, W. Lehnert (eds),
145 (1998) 414. Proceeding of the fifth International Symposium on Solid
[27] T. Tsai, S.A. Barnet, in: U. Stimming, S.C. Singhal, H. Oxide Fuel Cells, 1997, p. 61.
Tagawa, W. Lehnert (eds), Proceeding of the fifth Inter- [49] S.P.S Badwal, K. Foger, in: Proccedings of Third Eu-
national Symposium on Solid Oxide Fuel Cells, 1997, p. ropean Solid Oxide Fuel Cell Forum, Nantes, France,
274. 1998, p. 95.
[28] R. Cook, J.J. Qsborne, J.H. White, R.G. MacDuff, A.F. [50] R. Diethelm, M. Schmidt, B. Doggwiler, Th. Gamper, M.
Sammells, J. Electrochem. Soc. 129 (1992) L19. Keller, K. Honegger E. Batwai, in: Proceedings of the
[29] T. Ishihara, H. Matuda, Y. Takita, J. Am. Chem. Soc. Third European Solid Oxide Fuel Cell Forum, Nante,
116 (1994) 3801. . France, 1998, p. 87.
O. Yamamoto / Electrochimica Acta 45 (2000) 2423–2435 2435
[51] M. Aizawa, M. Kuroishi, H. Takeuchi, H. Tajiri, T. mamoto, H. Tagawa, S.C. Singhal (eds), Proceedings of
Nakayama, in: Abstracts of 1998 Fuel Cell Seminar, Fouth Internationa Symposium on Solid State Fuel
Palm Springs, USA, 1998, p. 270. Cells, Nagoya, Japan, Electrochem. Soc., NJ, USA,
[52] E.P. Murray, T. Tsai, S.A. Barnett, Nature 400 (1999) 1995 p. 781.
469. [54] N.Q. Minh, T. Takahashi, Science and Technology of
[53] R.T. Baker, I.S. Metcalfe, in: M. Dokiya, O. Ya- Ceramic Fuel Cells, Elsevier, Amsterdam, 1995.