1. We demonstrate the applicability of LAMOX oxide ion conductor as the electrolyte of single-chamber SOFC, using two compositions La 0.9 Dy 0.1 Mo 2 O 9 (LDM) and La 0.9 Dy 0.1 Mo 1 W 1 O 9 (LDMW55). The peak power of the SOFC based on La 0.9 Dy 0.1 Mo 2 O 9 is measured 220 mW cm -2 at 700  C in flowing methane/air mixture with CH 4 :O 2 =2:1. Despite its high ion conductivity, the applicability of LAMOX electrolyte has been questioned for a long time, because it is susceptible to hydrogen reduction, reacts with the typical cathode compositions, expands more than other typical electrolytes at 500 – 800  C. Single chamber SOFC based on LDMW electrolyte and its on-site anode initialization Dah-Shyang Tsai,* Jen-Chieh Lo, Yu-Chen Chen Department of Chemical Engineering, National Taiwan University of Science and Technology 43, Keelung Road, Section 4, Taipei 10607 Taiwan E-mail address: dstsai@mail.ntust.edu.tw ABSTRACT Introduction LAMOX stands for a group of oxygen ion conductors based on its parent crystal La 2 Mo 2 O 9. Featured with high oxygen ion conductivity in the temperature range of SOFC interest, the crystal structure of  -phase La 2 Mo 2 O 9 is intrinsically defective. Partially filled oxygen sites, O(2) and O(3), are approximately 2/3 and 1/3 filled. Most of O(3) sites surround Mo 6+, which is the key element for LAMOX. Meanwhile, the high valence Mo is also the reason for hydrogen reduction. Figure 2 Comparison of La 1.8 Dy 0.2 Mo 2 O 9 and La 1.8 Dy 0.2 Mo 1.6 W 0.4 O 9 microstructures, that were first reduced in 3% H 2 (97% Ar) at 600  C for 48 h then annealed in air at 1000  C to restore its microstructure. Before hydrogen reduction, the oxide surfaces were creamy white. Reduction at 600  C turned the surfaces into dark grey. Annealing in air can restore the color of oxide surface, but left with microscopic damages on the surface of La 1.8 Dy 0.2 Mo 2 O 9, Figure 2(a). For La 1.8 Dy 0.2 Mo 1.6 W 0.4 O 9, the microscopic damages are not found, Figure 2(b), showing the W substitution alleviates Mo reduction. Sr is a common element in typical cathode composition, but LAMOX reacts with Sr and form SrMoO 4 as low as 600  C. A ceria interlayer may act as diffusion barrier to block interdiffusion and solid-state reaction. Figure 3 Reaction between La 0.6 Sr 0.4 Co 0.8 Fe 0.2 O 3 (LSCF6482) and La 0.9 Dy 0.1 Mo0 1.6 W 0.4 O 9 (LDMW82) at 800  C for 6 h, (a) no reaction with a SDC interlayer in between, (b) a product layer between LSCF6482 and LDMW82. Note the grain coarsening of LSCF6482 and new phase of LDMW82 are accompanied with the product layer formation. Figure 4 Solid state reaction between 50% LDMW92 and 50% LSCF6482 powder compact, soaked at 800  C for 6 h. XRD patterns of (a) 50% LDMW92 and 50% LSCF6482 mixture, (b) LDMW82, (c) LSCF6482. Note that SrMoO 4 and Mo deficient LAMOX phase in the pattern (a). Figure 5 Thermal expansion of LDM and LDMW55 measured with dilatometry. High thermal expansion between 480 and 800  C is difficult to match with. The TEC value of GDC is  12 ppm K -1, that of NiO  14 ppm K -1, that of Ni metal  17 ppm K -1. Although NiO+GDC and Ni+GDC are thermochemically matched with LAMOX, the matching of thermal expansion is a headache. Figure 6 The experimental setup for measuring single chamber SOFC performance. The cell is housed in a quartz glass tube. The flowing CH 4 /Air is preheated before itmeets the cell, which is hanged on two gold wires connecting to the current collectors. Attempts to build the dual chamber SOFC have failed, mainly because of the difficulty in finding suitable gas sealants for LDMW electrolyte. However, we did succeed in fabricating the single chamber SOFC using the anode support design based on LAMOX electrolytes. Figure 7 Configuration of the anode-supported cell. The matching cathode LSCF6482 is interfaced with the i- GDC protected LAMOX (LDM or LDMW55). NiO+GDC (4:6 wt ratio) mechanically supports the cell. The electrolyte thickness  60  m. Figure 8 Plateform for SOFC measurement. Gas cylinders and mass flow controllers are placed at the right-hand side. The vacuum pump and the hydrogen detector are placed at the left-hand side. In between is the furnace and the quartz glass tube for housing the coin cell. Initialization of single chamber SOFC is critical to its measurement. We adopt the on-site initialization to reduce the anode with a minimum influence on the cathode. Condition for initialization: CH 4 /air (CH4:O2=2:1) flow rate 350 sccm at 650  C Figure 9 (a) Variation of cell voltage with time, (b) Incubation time versus the spacing between Ni+GDC and anode. Figure 10 I-V and I-P characteristics of the cell Ni+GDC/LDM/i-GDC/LSCF6482 in flowing CH4/air (CH4:O2=2:1). The flow rate is 350 sccm. Two temperature readings are given for each measurement, the one being parenthesized is the cell temperature; the other is the furnace temperature. Figure 11 I-V and I-P characteristics of the cell Ni+GDC/LDMW55/i-GDC/LSCF6482 in flowing CH4/air (CH4:O2=2:1). The flow rate is 350 sccm. Two temperature readings are given for each measurement, the one being parenthesized is the cell temperature; the other is the furnace temperature. Conclusions We have shown the LAMOX ion conductor can be the electrolyte of SOFC. Similar to the ion conductor family of ceria, its OCV value is less than 1.0 when the anode-supported single chamber SOFC based on LDMW is immersed in the CH4/air mixture flow with CH4:O2=2:1. Figure 1  -La 2 Mo 2 O 9 crystallizes in SnWO 4 structure with the unoccupied oxygen sites O(2) and O(3) to facilitate oxygen ion transport. Comparison of cation coordination environment indicates the 1/3 filled O(3) sites are closely associated with Mo 6+ ion. (J. Mater. Chem. 11, 2001, 119)