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Page 4 of 14 Zhuang et al. Energy Mater. 2025, 5, 500015 https://dx.doi.org/10.20517/energymater.2024.90

Figure 1. Schematic diagram of the synthesis process of BZCYG4411 powder using one-step SSR method with two types of raw
materials.

For type 2, the same one-step SSR synthesis method was adopted using the raw materials of BaCO , ZrO
3
2
(Aladdin, 99%, China), CeO (Aladdin, 99.99%, China), Y O , and Gd O (Aladdin, 99.99%, China).
3
2
3
2
2
Meanwhile, dense bars of BCZYG4411 were prepared by dry-pressing at the pressure of 200 MPa and
sintered at 1,250 °C for 5 h, which were used for the electrical conductivity, TEC, and linear shrinkage test.
For comparison, the commercial BZCYYb4411 (Ruier Powder Materials Corporation, China) was also
sintered at 1,100 °C for 10 h for achieving the desirable crystallinity.
The BSNCF oxide was synthesized using a conventional SSR method. The stoichiometric amounts of
BaCO , Sc O (Aladdin, 99.9%, China), Nb O (Aladdin, 99.99%, China), and Fe O (Aladdin, 99%, China)
3
3
2
2
2
3
5
powders were mixed and ball-milled in ethanol for 24 h at 400 r/min. Then the mixed powder was dried,
crushed, and calcined at 1,150 °C for 20 h to obtain pure BSNCF [31,32] . Additionally, the commonly used
PrBa Sr Co Fe O (PBSCF) cathode was also used for the performance comparison. The synthesis
0.5
0.5
0.5
1.5
6-δ
method can be observed in our previous work .
[20]
Preparation of anode-supported tubes by extrusion
The above synthesized BZCYG4411 (type 1) powder, nickel oxide (NiO, J.T. Baker, USA), the pore-forming
material of polymethyl methacrylate (PMMA, Aladdin, China), and ethanol were mixed in a mass ratio of
4:6:1:11 and ball-milled for 48 h at 300 r/min to obtain a well-dispersed mixed slurry. The slurry was then
dried at 80 °C to obtain the mixed powder for extrusion. Next, 1 kg of the primary anode support powder,
30 g of binder hydroxypropyl methylcellulose (HPMC, Aladdin, China), 20 g of plasticizer dioctyl phthalate
(DOP, Shanghai Sinopharm, AR, China), 15 g of lubricant tung oil (Aladdin, China), 20 g of dispersant
triethanolamine (TEA, Shanghai Sinopharm, AR, China), pH neutralizer 30 wt% aqueous citric acid
solution (Aladdin, 99.5%, China), and 200 g of deionized water were mixed in a powder kneader in turn for
5 h to obtain a homogenous mixture with adequate stickiness, plasticity, and pH-neutrality [33,34] . The mixed
mud was taken out and sealed using cling film and a sealed bag to prevent exposure to air. It was then
placed in a low-temperature, dark-location place for two days to undergo aging and obtain the desirable
mixed mud for extrusion.

The anode-supported tubes of the microtubular cells were prepared using the extrusion method, as shown
in Figure 2. The mixed mud was fed into the extrusion machine, with the extrusion rate at 0.5 cm s by
-1
adjusting the rotational speeds of the upper and lower shaft motors. Before extrusion, the mixed mud was
vacuum treated in the machine to remove any air bubbles. The extruded anode-supported tubes were dried
in an oven at 50 °C to remove moisture.