Evaluation of proton conducting BCY10-based anode supported cells by co-pressing method: Up-scaling, performances and durability

doi:10.1016/j.jpowsour.2013.12.082

Journal of Power Sources

Volume 255, 1 June 2014, Pages 302-307

https://doi.org/10.1016/j.jpowsour.2013.12.082 Get rights and content

Highlights

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Commercial powders produced at kilogram scale have been analysed and used.
•
The maximum power density of around 180 mW cm⁻² is obtained at 600 °C on both sizes.
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The co-pressing method is only efficient at the laboratory scale.

Abstract

One of the main target of the French ANR CONDOR (2009–2011) project coordinated by EDF-EIFER was the elaboration of proton conducting BaCe_0,9Y_0,1O_3−δ-based cells using processes suitable at industrial level. Thus, commercial powders produced at kilogram scale (anode, electrolyte and cathode) have been analysed and used. Then, elaboration of protonic ceramic half-cells by co-pressing method from 25 mm to 80 mm in diameter has been assessed in order to establish the suitability of this shaping method regarding industrial requirements. According to results, the co-pressing method is relevant for the elaboration of cells up to 40 mm in diameter (laboratory experiment). A sintering step was carried out to densify the electrolyte layer to get a gas-tight membrane. Nickelate-based cathodes were screen-printed and electrochemical performances of the final assembly have been measured. Electrical power up to 180 mW cm⁻² at 600 °C has been obtained on both 25 and 40 mm cells.

Introduction

The high energy conversion efficiency and the low impact to the environment are part of great advantages of Solid Oxide Fuel Cells (SOFCs), which are promising devices for electricity generation. They convert directly the chemical energy from the fuel to electricity. However, most of technical issues of SOFCs remain the high operating temperatures (>700 °C), leading to accelerated ageing of materials. During the last ten years, Protonic Ceramic Fuel Cell has considerably attracted attention thanks to the lower temperature range (400–600 °C) and the interest of a better energy efficiency with the non-dilution of the fuel since the water is produced to the air electrode side.

Since Iwahara published in the 80's his work on protonic perovskites as electrolyte for fuel cells [1], [2], [3], [4], many proton conducting oxide structures have been studied, like perovskites [5], [6], [7], [8], [9], [10], [11], based-perovskites (like Ba₃Ca_1,18Nb_1,82O₉ or BaIn_0,8Ti_0,2O_2,6□_0,4) [12], [13], [14], [15], ortho-niobates [16], [17], [18] and others candidates [19], [20], [21], [22].

Now, most of protons conducting ceramic cell researches are devoted to the optimization of their performances and reliability. This aspect request notably the strict reduction of ohmic resistance of each interface layers by promoting very thin and dense electrolyte layer [23], [24], [25], [26], a well-architecture anode functional layer to increase the triple-phase boundary (TPB) for hydrogen electrode reactions [27], [28] and a good chemical compatibility and microstructure for air electrodes side [29], [30], [31], [32].

But, until now, most of electrical performances related in the literature do refer to lab-scale size cell below 10 mm of diameter. Thus, no real investigations of efficient up scaling routes have been led until now in order to fit to the industrial requirements for the introduction of cells in stacks. This aspect appears fundamental to approach the stack manufacturing then the system integration key steps research in a reasonable term.

Here proposed is the assessment of co-pressing methods for an up-scaling of PCFC anode- supported cell manufacture. Microstructure and electrical performances of such cells are investigated.

Section snippets

Powders

All samples were prepared using commercial powders (Marion Technologies^®) produced at kilogram scale, listed below:

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Electrolytes: BaCe_0,9Y_0,1O_3−δ (BCY10)
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Anode (cermet): NiO–BaCe_0,9Y_0,1O_3−δ
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Cathode: Pr₂NiO_4 + δ

Cells elaboration

The half cells were made by co-pressing of powders (at AIME laboratory and Céramiques Techniques Industrielles CTI^®). In a first time, cermet spray-dried powder (NiO-BCY10) was pressed (100 MPa) into discs (−25–40–80 mm in diameter, 2 mm in thickness). Then, a given weight of electrolyte

Characterization of powders

As shown in Figs. 1 and 2, the as-prepared powders of BaCe_0,9Y_0,1O_3−δ and Pr₂NiO_4 + δ exhibit a well-developed crystallization and all the peaks can be well indexed as pure perovskite and Ruddlesden–Popper phases, respectively. It could be clearly seen that there is no evidence of the formation of other substances. All the XRD measurements made on the synthesized-phases are in agreement with the corresponding JCPDS card (n° 82–2372 for BaCe_0,9Y_0,1O_3−δ, n° 44–1159 for NiO, n° 34–1113 for Pr₂NiO

Conclusion

In this work, proton conducting ceramic oxide materials were synthesized. The up-scaling of powder synthesis at industrial scale was successfully performed, as well as increasing the size of cell from 25 to 40 mm in diameter. Afterwards, co-pressing method has been assessed to elaborate Proton conducting Ceramic Cells (PCC). Regarding feasibility and reproducibility, this shaping method is only efficient at the laboratory scale in order to evaluate quick performances of materials or assemblies

Acknowledgements

Funding by the Agence Nationale de la Recherche under the CONDOR project (ANR-08-PANH-004-01) is acknowledged with thanks. The authors would also like to thank industrial support from Flexitallic^® and Fiaxell^®.

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Anode-supported protonic ceramic fuel cells (PCFCs) have many advantages such as the excellent performance and durability at lower temperatures. However, the fabrication of large-area PCFCs is still a big challenge. In this work, the anode supported 10 × 10 cm² PCFCs with BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3-δ (BZCYYb) electrolyte are fabricated by an optimized sintering process combining with multilayer-tape casting and hot-pressing lamination technology. Through optimizing the sintering shrinkage and thermal expansion behavior, anode supported large-area PCFCs with dense BZCYYb electrolyte are obtained with optimal sintering process. The maximum power density of the cell using H₂ as fuel reaches 400 mW/cm² at 700 ℃. The cell also shows a good thermal cycling performance and durability in 425 h test. Preliminary experimental results indicate that the fabrication technology with multilayer-tape casting and hot-pressing lamination is successful for large-area PCFCs, which can improve the cell fabrication efficiency and provide positive reference for large-area PCFCs.
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In this work, we report the spray coating, a simple and effective method, to prepare proton conducting BaCe_0.7Zr_0.1Y_0.2O₃ (BCZY) membranes on the pre-annealed porous anode substrates. The effects of sintering temperature on the electrolyte membrane and anode microstructure, proton conductivities of the resulted thin films, and their fuel cell performances in H₂/air were investigated. Dense BCZY membranes with improved anode microstructure and good proton conductivity have been successfully obtained at reduced temperature using ZnO sintering aid. SOFCs using spray-coated electrolyte thin films gave a stable OCV value of 1.03 V and a maximum power density of 362 mW cm⁻² at 650 °C when operated using hydrogen as fuel and air as the oxidant.

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Short communicationEvaluation of proton conducting BCY10-based anode supported cells by co-pressing method: Up-scaling, performances and durability

Highlights

Abstract

Introduction

Section snippets

Powders

Cells elaboration

Characterization of powders

Conclusion

Acknowledgements

Solid State Ionics

Solid State Ionics

Solid State Ionics

Solid State Ionics

Solid State Ionics

Solid State Ionics

J. Solid State Chem.

Solid State Ionics

Solid State Ionics

Solid State Ionics

Solid State Ionics

J. Power Sources

Solid State Ionics

Solid State Ionics

Solid State Ionics

J. Solid State Chem.

J. Alloys Compd.

Electrochim. Acta

Ceram. Int.

Short communication
Evaluation of proton conducting BCY10-based anode supported cells by co-pressing method: Up-scaling, performances and durability