High-performance novel anode-supported microtubular protonic ceramic fuel cells via highly efficient and simplified extrusion technology
0 Abstract
Protonic ceramic fuel cells (PCFCs) are regarded as efficient energy conversion devices for addressing the challenges of carbon neutrality, which can directly convert the chemical fuel energy into electricity at reduced operating temperatures below 700 °C. However, the insufficient strength and immature preparation processes of PCFCs limit their practical application. In this work, the novel anode-supported microtubular PCFCs with a tube diameter of less than 5 mm were successfully prepared by extrusion technology combined with a dip-coating method. The newly developed BaZr0.4Ce0.4Y0.1Gd0.1O3-δ (BZCYG4411) proton-conducting electrolyte was synthesized using an extremely simple and efficient one-step solid-state reaction method, showing comparable electrical conductivity with BaZr0.4Ce0.4Y0.1Yb0.1O3-δ (BZCYYb4411) and BaZr0.1Ce0.7Y0.1Yb0.1O3-δ (BZCYYb1711) electrolytes, as well as excellent chemical stability. The single cell with Ba2Sc0.1Nb0.1Co1.5Fe0.3O6-δ (BSNCF) cathode exhibited a high peak power density of 906.86 mW cm-2 at 700 °C. Additionally, this microtubular PCFC demonstrated excellent stability after about 103 h durability test at a constant current of 0.5 A cm-2 at 650 °C. This study provides a highly efficient and simplified technology for fabricating high-performance and durable anode-supported microtubular PCFCs.
Keywords
INTRODUCTION
Energy and environmental issues have become increasingly prominent in recent years[1]. Developing highly efficient, sustainable, and clean technologies is a top priority to achieve the goals of carbon neutrality and sustainable development. Compared to conventional coal-based thermal power generation technology, fuel cells are power generators that can convert the chemical energy in the fuels directly into electricity through electrochemical reactions. Unlike conventional systems limited by the Carnot cycle, fuel cells can achieve high energy conversion efficiency[2]. Among all fuel cell systems, solid oxide fuel cells (SOFCs) are the most promising electrochemical conversion devices due to their high efficiency, reliance on non-precious metal catalyst, and all-solid-state structure[3,4]. SOFCs generally can be divided into two categories according to the mobile carriers. The first one is oxygen ion-conducting SOFCs (called O-SOFCs), and the second one is proton-conducting ceramic fuel cells [named H-SOFCs or protonic ceramic fuel cells (PCFCs)][5]. Yttrium-stabilized zirconia (YSZ) and scandium-stabilized zirconia (SSZ) are the commonly used oxygen ion-conducting electrolytes for O-SOFCs. They have a higher activation energy (Ea, ~0.9 eV) for oxygen ion conduction and typically operate at a higher temperature (700-1,000 °C), owning to the larger ionic radius of the oxygen ions[6,7]. In contrast, the carrier of PCFCs, proton (H+), has a much smaller radius and needs lower Ea (0.3~0.5 eV), making it possible to operate at low temperatures (< 700 °C)[8]. A lower operating temperature can effectively reduce the cost of accessory materials and improve the thermo-mechanical stability of the cell. In addition, water is generated on the cathode side of PCFCs, which helps to avoid the fuel dilution and improves the fuel utility[9-11].
To date, both planar and tubular PCFCs have been widely investigated and significant improvements reported[12]. Compared to planar PCFCs, tubular PCFCs have been receiving increasing attention because of their advantages of high mechanical strength, fast start-up, easy sealing, and good thermal cycle stability[13]. However, tubular PCFCs typically exhibit low power density due to the elongated current path, which increases the internal resistance[14]. The microtubular structure combines the advantages of both tubular and planar, featuring a smaller tube radius and shorter current channels, effectively reducing the loss for current collection and transmission, ultimately enhancing cell performance[15,16]. At the same time, the smaller size minimizes the impact of stresses from thermal gradients, allowing for rapid start-up, better mechanical strength, and low thermal shock damage[17]. However, most existing research has been focused on planar PCFCs, while there is little information available on developing microtubular PCFCs.
For the fabrication of anode functional layer (AFL) and electrolyte layer of microtubular PCFCs, the dip-coating method is one of the most commonly used techniques, which only requires one to three dip-coating cycles to achieve the desired thickness (10-30 μm). However, for the anode supports, which play a critical role in supporting the whole cell structure, it need to reach a certain thickness of around hundred microns. Currently, several techniques have been used for the thick anode support fabrication of microtubular PCFCs, such as phase inversion, dip-coating, and 3D printing. Hou et al. fabricated a high-performance microtubular PCFC with an outer cell diameter of 0.38 mm via phase inversion method (support layer) combined with a dip-coating process (electrolyte layer), achieving a maximum power density of 2.62 W cm-2 at 700 °C[18]. Tong et al. also developed a phase inversion method for the batch preparation of microtubular PCFCs with an extremely small outer diameter of 0.15 mm, showing a maximum power density of
The commonly used proton-conducting electrolytes, such as
In this work, a novel
EXPERIMENTAL
Synthesis of electrolyte and cathode powders
The BZCYG4411 oxide was synthesized using a one-step SSR method using two types of raw materials. For type 1, BaCO3 (Shanghai Aladdin Biochemical Technology Co., Ltd., 99.95%, China), GDC20 (Ruier Powder Materials Corporation, China), 8YSZ (Sinocera, China), and Y2O3 (Aladdin, 99.99%, China) were weighed and mixed according to the stoichiometric ratio, followed by ball-milling in ethanol for 24 h at 300 r/min. Then the mixture was completely dried at 80 °C in an oven. Subsequently, the dry powder was pressed into large pellets at 10 MPa with a diameter of 20 mm and then calcined at 1,200 °C for 12 h to obtain pure BZCYG4411 [Figure 1]. The reaction equation is given in
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 BaCO3, ZrO2 (Aladdin, 99%, China), CeO2 (Aladdin, 99.99%, China), Y2O3, and Gd2O3 (Aladdin, 99.99%, China). 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 BaCO3, Sc2O3 (Aladdin, 99.9%, China), Nb2O5 (Aladdin, 99.99%, China), and Fe2O3 (Aladdin, 99%, China) 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 PrBa0.5Sr0.5Co1.5Fe0.5O6-δ (PBSCF) cathode was also used for the performance comparison. The synthesis 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-1 by 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.
Figure 2. Schematic preparation process of microtubular PCFCs.
Preparation of microtubular PCFCs
The schematic drawing illustrating the preparation process of microtubular PCFCs is presented in Figure 2. Firstly, the NiO-BZCYG4411 tubes were calcined at 1,000 °C for 2 h to remove the organic solvents. Secondly, the AFL slurry was prepared by ball-milling 10 g of NiO, 10 g of commercial BZCYYb1711 (Ruier Powder Materials Corporation, China), and 0.6 g of polyvinyl pyrrolidone (PVP, K30, Aladdin, China) in
The BSNCF/PBSCF cathode slurry was prepared by mixing an equal mass of 5 wt% ethyl cellulose-terpineol solution (Shanghai Sinopharm, AR, China), which was then milled for 12 h. The cathode slurry was applied to the surface of the BZCYYb1711 electrolyte and dried at 80 °C in an oven, followed by sintering at 950 °C for 3 h to obtain the full microtubular PCFCs.
Electrochemical performance test
The fabricated microtubular PCFCs were cut into smaller pieces (about 2 cm) with an effective cathode area of 0.7 cm2. The open circuit voltage (OCV), current-voltage-power (I-V-P) and electrochemical impedance spectra (EIS) curves of microtubular PCFCs were examined using the electrochemical workstation (BioLogic SP-300, France). The cell was tested with 3% humidified H2 (40 mL/min) as the fuel and ambient air as the oxidant. The frequency range was set from 0.1 Hz to 100 kHz with a 10 mV AC signal. The surfaces of the anode and cathode were connected with silver wires using a silver paste (DAD-87) respectively to collect current. A ceramic adhesive (Ceramabond 552, Aremco Products Inc.) was used for sealing the microtubular PCFCs.
Characterization
The phase structure of the electrolyte and cathode powders was characterized by X-ray diffraction (XRD, Bruker D8 Advance, Germany). The high-resolution image, diffraction pattern, and element distribution of BZCYG4411 powder was characterized using high-resolution transmission electron microscopy (HR-TEM, FEI talos F200x G2, USA) equipped with energy-dispersive X-ray (EDX) mapping. The powder of BZCYG4411 and the surface and cross-sectional microstructure of microtubular PCFCs were observed using field scanning electron microscopy (FSEM, TESCAN MAIA3 LMH, Czech). The electrical conductivity of BZCYG4411 was measured by four-probe direct current (DC) method from 500 to 700 °C using the electrochemical workstation. The TEC and linear shrinkage of samples were evaluated in ambient air using the dilatometer (DIL 402 C, NETZSCH).
RESULTS AND DISCUSSION
Characterization of electrolytes and cathode
Figure 3A presents the XRD patterns of BZCYG4411 oxide (type 1) prepared by the one-step SSR method and commercial BZCYYb4411 oxide. The BZCYYG4411 exhibits eight broad peaks at 29.25°, 36.00°, 41.85°, 51.89°, 60.71°, 68.86°, 76.49°, and 83.96°, corresponding to the (110), (111), (200), (211), (220), (310), (222), and (321) crystal planes, respectively. These peaks matched well with the BZCYY4411 oxide and
Figure 3. (A) XRD patterns of BZCYG4411 and commercial BZCYYb4411; (B) Rietveld refinement profiles of BZCYG4411; (C) HR-TEM image and (D) EDX mapping results of BZCYG4411.
Figure 4A shows the electrical conductivity of BZCYG4411 measured by four-probe DC method at
Figure 4. (A) The electrical conductivity comparison of BZCYG4411 and other reported electrolytes; (B) Arrhenius plots of electrical conductivity of BZCYG4411 measured at 500-700 °C; (C) The TECs of BZCYG4411 and NiO-BZCYG4411 anode support measured at room temperature to 1,000 °C; (D) The linear shrinkages of the BZCYG4411 and NiO-BZCYG4411 versus temperature.
where σion is ionic conductivity and σelectron is the electronic conductivity. The calculated transference numbers are displayed in Supplementary Figure 4B, showing a gradual decrease in ionic conductivity and a corresponding increase in electronic conductivity as the temperature rises.
In order to ensure the effectiveness of the sintering procedure, the thermal behavior of BZCYG4411 and NiO-BZCYG4411 (6:4) dense bars was also evaluated. The TECs of NiO-BZCYG4411 anode support and BZCYG4411 measured from room temperature to 1,000 °C are shown in Figure 4C. The average TEC of BZCYG4411 is 10.64 × 10-6 K-1, which is similar to that of BZCYYb1711[41]. The average TEC of NiO-BZCYG4411 anode support is 11.03 × 10-6 K-1, which is also comparable with the protonic electrolytes. This compatibility helps avoid separation or cracking during the co-sintering process of the cells. Additionally, the sintering shrinkage behavior of NiO-BZCYG4411 anode support and BZCYG4411 electrolyte is presented in Figure 4D. They both had a smaller degree of shrinkage until 1,010.36 °C. The shrinkage of Ni-BZCYG4411 anode support occurs earlier than the shrinkage of BZCYYb1711 (at 1,155 °C), which may facilitate the densification of electrolyte[41,42].
The matched thermal properties between the electrolyte and cathode materials are the crucial factors influencing the thermal-mechanical stability of PCFCs. Considering the special structure of microtubular PCFCs, the matching of thermal properties becomes more important, so a new low thermal expansion material, BSNCF oxides, was selected. Figure 5A shows the XRD pattern of BSNCF obtained using the SSR method and sintered at 1,150 °C for 20 h, indicating a pure phase with a typical double-perovskite crystal structure. Figure 5B shows the TEC of BSNCF measured from room temperature to 1,000 °C. The TEC value of BSNCF is 13.9 × 10-6 K-1, significantly lower than that of PBSCF oxide[43]. Figure 5C compares the TEC values of BZCYYb1711 and other Co-based or new cathode materials, such as La0.6Sr0.4Co0.8Fe0.2O3-δ (LSCF, 21.4 ×10-6 K-1)[44], Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF, 23.6 ×10-6 K-1)[45], Ba0.95La0.05Fe0.8Zn0.2O3-δ (BLFZ,
Figure 5. (A) XRD pattern of BSNCF; (B) The TEC of BSNCF measured at room temperature to 1,000 °C; (C) The TECs comparison of BZCYYb1711 electrolyte with other commonly used cathode materials.
Electrochemical performance and stability
Figure 6 summarizes the electrochemical performance and stability of the microtubular PCFC with BSNCF cathodes. The I-V-P curves of the single cell measured at different temperatures are shown in Figure 6A. The OCVs were 1.002, 1.040, and 1.085 V at 700, 650, and 600 °C, respectively, which are close to the theoretical values, indicating that the electrolyte is dense[48]. The PPDs of 906.86, 655.56, and
Figure 6. The electrochemical performance of the microtubular PCFC with BSNCF cathode. (A) I-V-P curves; (B) EIS curves; (C) Stability test at 650 °C; (D) DRT analysis of the cell before and after the durability test.
PPDs of tubular PCFCs via the extrusion technology
| Outer diameter (mm) | Electrolyte (thickness) | Cathode | Temperature (°C) | PPDs (mW cm-2) | Ref. |
| 8.2 | BZCYYb (~15 μm) | BCFZY | 600 | 517 | [34] |
| 8.2 | BZCYYb (~15 μm) | BSCF | 600 | 534 | [34] |
| 8.2 | BZCYYb (~15 μm) | PBSCF | 600 | 326 | [34] |
| 9.3 | BZCY (~10 μm) | LSCF-BZCY | 600 | 300 | [26] |
| – | BZCYYb (~20 μm) | PNOF-BZCYYb | 600 | 390 | [54] |
| 5.0 | BZI | LSCF | 600 | 143 | [55] |
| 4.8 | BZCYYb (~15 μm) | BSNCF | 600 | 449.94 | This work |
| 4.8 | BZCYYb (~20 μm) | PBSCF | 600 | 546.61 | This work |
To further understand the possible causes of degradation, the distribution of relaxation time (DRT) was used to analyze the EIS variations of the cell before and after the durability test. Figure 6D shows four typical DRT peaks from low to high frequencies, denoted as P1, P2, P3, and P4, which represent the four main steps in the electrode reaction process of the cells[50]. The P1 peak in the low-frequency region is mainly related to gas diffusion in the electrode of the cell, and the P2 peak in the mid-frequency region is closely related to the oxygen reduction reaction (ORR) and oxygen-ion transport at the three-phase-boundary (TPB) interface, whereas the P3 peak in the mid- to high-frequency region is related to the formation and diffusion of protons in the anode, and the P4 peak in the high-frequency region represents the process of electron transfer and ion transfer through the interface between the electrolyte and the electrode[51-53]. After the stability test, the P2-P4 peaks showed slight increases, indicating a deterioration in the ORR process, which may result from competition between the generated water and oxygen absorption as explained previously.
In addition, the electrochemical performance of microtubular PCFC with PBSCF cathode is also evaluated, as shown in Supplementary Figure 6A and B. The PPDs of 546.61 and 866.71 mW cm-2 were obtained at 600 and 650 °C, respectively. These results represent the highest performance compared to other previously reported tubular PCFCs fabricated by extrusion, as summarized in Table 1. The corresponding Ro were 0.28 and 0.22 Ω cm2, respectively, and Rp were 0.16 and 0.07 Ω cm2. Supplementary Figure 6C shows the good long-term stability of the cell under a constant current of 0.5 A cm-2 at 650 °C for 105 h, further confirming the good stability of microtubular PCFC prepared by extrusion technology. Meanwhile, the cell performance of tubular PCFC fabricated by different techniques is summarized in Supplementary Table 2, such as extrusion, 3D printing, and phase inversion, highlighting the excellent electrochemical performance of PCFC fabricated by extrusion technique.
Morphology of microtubular PCFC
Figure 7A shows the overall physical picture of the microtubular PCFC. The structure of PCFCs plays a crucial role in their performance and stability. As shown in Figure 7B, the three layers of the porous anode, electrolyte, and cathode remained intact and well-bonded. Figure 7C shows the surface of the electrolyte, displaying a desirable dense structure. Figure 7D shows the cross-sectional image of the microtubular PCFC with the Ni-BZCYG4411|Ni-BZCYYb1711|BZCYYb1711|BSNCF configuration after the stability test. The cell exhibits excellent structural integrity, and the dense BZCYYb1711 electrolyte effectively prevents gas leakage. The Ni-BZCYG4411 anode support is illustrated in Figure 7E, showing a uniform distribution of Ni and BZCYG4411 particles after the durability test. Finally, Figure 7F shows the morphology of BSNCF cathodes with porous structure. The large particle size might be due to high-temperature sintering during the synthesis process of SSR.
Figure 7. Structure of microtubular PCFCs. (A) Physical drawing of the microtubular PCFC; (B) the SEM cross-sectional image of the cell consisting of Ni-BZCYG4411 anode support| Ni-BZCYYb1711 functional layer|BZCYYb1711 electrolyte|cathode; (C) The electrolyte surface; (D) Typical cross-sectional SEM image of the microtubular PCFC with BSNCF; (E) The Ni-BZCYG4411 anode support after the stability test; (F) Morphology of PBSCF cathode.
CONCLUSIONS
In this work, a novel anode-supported microtubular PCFC with a tube diameter of less than 5 mm was successfully fabricated using extrusion technology combined with dip-coating process. The microtubular PCFC exhibited good mechanical strength during testing. The newly developed BZCYG4411 proton-conducting electrolyte was synthesized using a novel one-step SSR method, showing comparable electrical conductivity with BZCYYb4411 and BZCYYb1711 electrolytes, along with excellent chemical stability in
DECLARATIONS
Acknowledgments
The authors acknowledge the financial support provided by the National Natural Science Foundation of China (U2005215), Anhui Province Science and Technology Major Project (202203a07020028), China Postdoctoral Science Foundation (2023M743769), and Science and Technology Program of Xuzhou (KC22017).
Authors’ contributions
Conceived the research, designed the experiments and prepared cells: Zhuang, Z.; Huang, Z.
Powder synthesis and conductivity test: Zhang, X.; Liu, K.; Zheng, G.
Discussed and revised the manuscript: Chen, T.; Sun, R.; Xu, L.; Wang, S.
All authors contributed to revising the manuscript.
Availability of data and materials
Data supporting the results of this study are available from the corresponding author upon request.
Financial support and sponsorship
The work was financially supported by the National Natural Science Foundation of China (U2005215), Anhui Province Science and Technology Major Project (202203a07020028), China Postdoctoral Science Foundation (2023M743769), and Science and Technology Program of Xuzhou (KC22017).
Conflicts of interest
All authors declared that there are no conflicts of interest.
Ethical approval and consent to participate
Not applicable.
Consent for publication
Not applicable.
Copyright
© The Author(s) 2025.
Supplementary Materials
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Zhuang, Z.; Huang, Z.; Zhang, X.; Liu, K.; Zheng, G.; Chen, T.; Sun, R.; Xu, L.; Wang, S. High-performance novel anode-supported microtubular protonic ceramic fuel cells via highly efficient and simplified extrusion technology. Energy Mater. 2025, 5, 500015. http://dx.doi.org/10.20517/energymater.2024.90
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