Pyrochlore La2Zr2–xNixO7 anodes for direct ammonia solid oxide fuel cells

doi:10.1007/s11708-024-0948-2

Front. Energy

2024, Vol. 18

Issue (5) : 699-711 https://doi.org/10.1007/s11708-024-0948-2

Pyrochlore La₂Zr_2–xNi_xO₇ anodes for direct ammonia solid oxide fuel cells

Shiqing Yang, Yijie Gao, Xinmin Wang, Fulan Zhong(

), Huihuang Fang, Yu Luo(

), Lilong Jiang

National Engineering Research Center of Chemical Fertilizer Catalyst (NERC-CFC), College of Chemical Engineering, Fuzhou University, Fuzhou 350002, China

Download: PDF(5183 KB) HTML
Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks

Abstract

Developing efficient anode catalysts for direct ammonia solid oxide fuel cells (NH₃-SOFCs) under intermediate-temperatures is of great importance, in support of hydrogen economy via ammonia utilization. In the present work, the pyrochlore-type La₂Zr_2–xNi_xO_7+δ (LZN_x, x = 0, 0.02, 0.05, 0.08, 0.10) oxides were synthesized as potential anode catalysts of NH₃-SOFCs due to the abundant Frankel defect that contributes to the good conductivity and oxygen ion mobility capacity. The effects of different content of Ni²⁺ doping on the crystal structure, surface morphology, thermal matching with YSZ (Yttria-stabilized zirconia), conductivity, and electrochemical performance of pyrochlore oxides were examined using different characterization techniques. The findings indicate that the LZN_x oxide behaves as an n-type semiconductor and exhibits an excellent high-temperature chemical compatibility and thermal matching with the YSZ electrolyte. Furthermore, LZN_0.05 exhibits the smallest conductive band potential and bandgap, making it have a higher power density as anode material for NH₃-SOFCs compared to other anodes. As a result, the maximum power density of the LZN_0.05-40YSZ composite anode reaches 100.86 mW/cm² at 800 °C, which is 1.8 times greater than that of NiO-based NH₃-SOFCs (56.75 mW/cm²) under identical flow rate and temperature conditions. The extended durability indicates that the NH₃-SOFCs utilizing the LZN_0.05-40YSZ composite anode exhibits a negligible voltage degradation following uninterrupted operation at 800 °C for 100 h.

Keywords anode catalyst ammonia oxidation Ni particles NH₃-SOFCs

Corresponding Author(s): Fulan Zhong,Yu Luo

Online First Date: 03 June 2024 Issue Date: 16 October 2024

Cite this article:

Shiqing Yang,Yijie Gao,Xinmin Wang, et al. Pyrochlore La₂Zr_2–xNi_xO₇ anodes for direct ammonia solid oxide fuel cells[J]. Front. Energy, 2024, 18(5): 699-711.

URL:

https://academic.hep.com.cn/fie/EN/10.1007/s11708-024-0948-2
https://academic.hep.com.cn/fie/EN/Y2024/V18/I5/699

Fig.1 Synthesis and utilization of green ammonia.

Fig.2 Compatibility analysis.

Fig.3 Oxygen vacancy and conductivity analysis.

Fig.4 UV-vis diffuse reflectance spectroscopy.

Fig.5 Electrical conductivity analysis.

Fig.6 Electrochemical activity.

Fig.7 Ammonia decomposition and electrochemical activity.

Fig.8 Stability of the single cell at 50 mA/cm² and 800 °C.

Fig.9 DRT analysis.

Fig.10 Schematic of NH₃-SOFCs with LZN_x-YSZ as anode.

1	M Ni, M Leung, Y C Leung. Ammonia-fed solid oxide fuel cells for power generation—A review. International Journal of Energy Research, 2009, 33(11): 943–959 https://doi.org/10.1002/er.1588
2	M Ni, M Leung, K Sumathy. et al.. Potential of renewable hydrogen production for energy supply in Hong Kong. International Journal of Hydrogen Energy, 2006, 31(10): 1401–1412 https://doi.org/10.1016/j.ijhydene.2005.11.005
3	P E Dodds, I Staffell, A D Hawkes. et al.. Hydrogen and fuel cell technologies for heating: A review. International Journal of Hydrogen Energy, 2015, 40(5): 2065–2083 https://doi.org/10.1016/j.ijhydene.2014.11.059
4	R Estevez, F J López-Tenllado, L Aguado-Deblas. et al.. Current research on green ammonia (NH3) as a potential vector energy for power storage and engine fuels: A review. Energies, 2023, 16(14): 5451–5484 https://doi.org/10.3390/en16145451
5	Y Zheng, C Zhao, T Wu. et al.. Enhanced oxygen reduction kinetics by a porous heterostructured cathode for intermediate temperature solid oxide fuel cells. Energy and AI, 2020, 2: 100027 https://doi.org/10.1016/j.egyai.2020.100027
6	M Zhang, M Hashinokuchi, R Yokochi. et al.. Effect of Infiltrated transition metals in Ni/Sm-doped CeO2 cermets anode in direct NH3-fueled SOFCs. ECS Transactions, 2017, 78(1): 1517–1522 https://doi.org/10.1149/07801.1517ecst
7	X Jia, F Lu, K Liu. et al.. Improved performance of IT-SOFC by negative thermal expansion Sm0.85Zn0.15MnO3 addition in Ba0.5Sr0.5Fe0.8Cu0.1Ti0.1O3-cathode. Journal of Physics Condensed Matter, 2022, 34(18): 184001 https://doi.org/10.1088/1361-648X/ac4fe7
8	L Bi, E Fabbri, E Traversa. Solid oxide fuel cells with proton-conducting La0.99Ca0.01NbO4 electrolyte. Electrochimica Acta, 2018, 260: 748–754 https://doi.org/10.1016/j.electacta.2017.12.030
9	J G Lee, J H Park, Y G Shul. Tailoring gadolinium-doped ceria-based solid oxide fuel cells to achieve 2 W/cm2 at 550 °C. Nature Communications, 2014, 5(1): 4045 https://doi.org/10.1038/ncomms5045
10	C J Winter. Hydrogen energy—Abundant, efficient, clean: A debate over the energy-system-of-change. International Journal of Hydrogen Energy, 2009, 34(14): S1–S52 https://doi.org/10.1016/j.ijhydene.2009.05.063
11	Y Song, H Li, M Xu. et al.. Infiltrated NiCo alloy nanoparticle decorated perovskite oxide: A highly active, stable, and antisintering anode for direct-ammonia solid oxide fuel cells. Small, 2020, 16(28): 2001859 https://doi.org/10.1002/smll.202001859
12	Y Zheng, Y Li, T Wu. et al.. Controlling crystal orientation in multilayered heterostructures toward high electro-catalytic activity for oxygen reduction reaction. Nano Energy, 2019, 62: 521–529 https://doi.org/10.1016/j.nanoen.2019.05.069
13	L Lu, Y Liu, H Zhang. et al.. Exploring the potential of triple conducting perovskite cathodes for high-performance solid oxide fuel cells: A comprehensive review. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2023, 11(44): 23613–23639 https://doi.org/10.1039/D3TA05035A
14	J O Jensen, A P Vestbø, Q Li, et al. The energy efficiency of onboard hydrogen storage. Journal of Alloys and Compounds, 2007, 446–447: 723–728 10.1016/j.jallcom.2007.04.051
15	F Li, Y Li, H Chen. et al.. Impact of strain-induced changes in defect chemistry on catalytic activity of Nd2NiO4+δ electrodes. ACS Applied Materials & Interfaces, 2018, 10: 36926–36932 https://doi.org/10.1021/acsami.8b11877
16	A Molouk, J Yang, T Okanishi. et al.. Comparative study on ammonia oxidation over Ni-based cermet anodes for solid oxide fuel cells. Journal of Power Sources, 2016, 305: 72–79 https://doi.org/10.1016/j.jpowsour.2015.11.085
17	M Hashinokuchi, M Zhang, R Yokochi. et al.. Enhanced activity and stability of Ni-based binary anode in direct NH3-fueled SOFCs. ECS Transactions, 2017, 78(1): 1495–1500 https://doi.org/10.1149/07801.1495ecst
18	Y Zheng, C Zhao, Y Li. et al.. Directly visualizing and exploring local heterointerface with high electro-catalytic activity. Nano Energy, 2020, 78: 105236 https://doi.org/10.1016/j.nanoen.2020.105236
19	K Teramoto, H Iwai, M Kishimoto. et al.. Direct reforming of methane-ammonia mixed fuel on Ni-YSZ anode of solid oxide fuel cells. International Journal of Hydrogen Energy, 2020, 45(15): 8965–8974 https://doi.org/10.1016/j.ijhydene.2020.01.073
20	Y Li, W Zhang, T Wu, et al. Segregation induced self-assembly of highly active perovskite for rapid oxygen reduction reaction. Advanced Energy Materials, 2018: 1801893 10.1002/aenm.201801893
21	A Fuerte, R X Valenzuela, M J Escudero. et al.. Ammonia as efficient fuel for SOFC. Journal of Power Sources, 2009, 192(1): 170–174 https://doi.org/10.1016/j.jpowsour.2008.11.037
22	W Wang, C Su, Y Wu. et al.. Progress in solid oxide fuel cells with nickel-based anodes operating on methane and related fuels. Chemical Reviews, 2013, 113(10): 8104–8151 https://doi.org/10.1021/cr300491e
23	J Cao, Y Li, Y Zheng. et al.. A novel solid oxide electrolysis cell with micro-/nano channel anode for electrolysis at ultra-high current density over 5 A/cm2. Advanced Energy Materials, 2022, 12: 2200899 https://doi.org/10.1002/aenm.202200899
24	E Brightman, D G Ivey, D J L Brett. et al.. The effect of current density on H2S-poisoning of nickel-based solid oxide fuel cell anodes. Journal of Power Sources, 2011, 196(17): 7182–7187 https://doi.org/10.1016/j.jpowsour.2010.09.089
25	A Molouk, J Yang, T Okanishi. et al.. Electrochemical and catalytic behavior of Ni-based cermet anode for ammonia-fueled SOFCs. ECS Transactions, 2015, 68(1): 2751–2762 https://doi.org/10.1149/06801.2751ecst
26	V Kahlenberg, H Böhm. X-ray diffraction investigation of the defect pyrochlore Bi1.61Zn0.18Ti1.94V0.06O6.62. Journal of Alloys and Compounds, 1995, 223(1): 142–146 https://doi.org/10.1016/0925-8388(94)01479-5
27	J Xu, L Peng, X Fang. et al.. Developing reactive catalysts for low temperature oxidative coupling of methane: On the factors deciding the reaction performance of Ln2Ce2O7 with different rare earth A sites. Applied Catalysis A, General, 2018, 552: 117–128 https://doi.org/10.1016/j.apcata.2018.01.004
28	M Matsumoto, K Aoyama, H Matsubara. et al.. Thermal conductivity and phase stability of plasma sprayed ZrO2-Y2O3-La2O3 coatings. Surface and Coatings Technology, 2005, 194(1): 31–35 https://doi.org/10.1016/j.surfcoat.2004.04.078
29	Y Guo, W He, H Guo. Thermal-physical and mechanical properties of Yb2O3 and Sc2O3 co-doped Gd2Zr2O7 ceramics. Ceramics International, 2020, 46(11): 18888–18894 https://doi.org/10.1016/j.ceramint.2020.04.209
30	J Mizusaki, M Yoshihiro, S Yamauchi. et al.. Nonstoichiometry and defect structure of the perovskite-type oxides La1–xSrxFeO3. Journal of Solid State Chemistry, 1985, 58(2): 257–266 https://doi.org/10.1016/0022-4596(85)90243-9
31	K Shimamura, T Arima, K Idemitsu. et al.. Thermophysical properties of rare-earth-stabilized zirconia and zirconate pyrochlores as surrogates for actinide-doped zirconia. International Journal of Thermophysics, 2007, 28(3): 1074–1084 https://doi.org/10.1007/s10765-007-0232-9
32	M Glerup, O F Nielsen, F W Poulsen. The structural transformation from the pyrochlore structure A2B2O7 to the fluorite structure AO2 studied by Raman spectroscopy and defect chemistry modeling. Journal of Solid State Chemistry, 2001, 160(1): 25–32 https://doi.org/10.1006/jssc.2000.9142
33	B Mandal, P Krishna, A Tyagi. Order–disorder transition in the Nd2−yYyZr2O7 system: Probed by X-ray diffraction and Raman spectroscopy. Journal of Solid State Chemistry, 2010, 183(1): 41–45 https://doi.org/10.1016/j.jssc.2009.10.010
34	L Kong, I Karatchevtseva, D J Gregg. et al.. A novel chemical route to prepare La2Zr2O7 pyrochlore. Journal of the American Ceramic Society, 2013, 96(3): 935–941 https://doi.org/10.1111/jace.12060
35	S Lü, Y Zhu, X Fu. et al.. A-site deficient Fe-based double perovskite oxides PrxBaFe2O5+δ as cathodes for solid oxide fuel cells. Journal of Alloys and Compounds, 2022, 911: 165002 https://doi.org/10.1016/j.jallcom.2022.165002
36	J Feng, B Xiao, R Zhou. et al.. Thermal expansion and conductivity of RE2Sn2O7 (RE = La, Nd, Sm, Gd, Er and Yb) pyrochlores. Scripta Materialia, 2013, 69(5): 401–404 https://doi.org/10.1016/j.scriptamat.2013.05.030
37	Q Fan, F Zhang, F Wang. et al.. Molecular dynamics calculation of thermal expansion coefficient of a series of rare-earth zirconates. Computational Materials Science, 2009, 46(3): 716–719 https://doi.org/10.1016/j.commatsci.2009.02.033
38	R A Miller. Thermal barrier coatings for aircraft engines: History and directions. Journal of Thermal Spray Technology, 1997, 6: 35–42 https://doi.org/10.1007/BF02646310
39	I Stefaniuk. Electron paramagnetic resonance study of impurities and point defects in oxide crystals. Opto-Electronics Review, 2018, 26(2): 81–91 https://doi.org/10.1016/j.opelre.2018.02.002
40	W Wang, Y Yang, D Huan. et al.. An excellent OER electrocatalyst of cubic SrCoO3–δ prepared by a simple F-doping strategy. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2019, 7(20): 12538–12546 https://doi.org/10.1039/C9TA03099A
41	T Araya, M Jia, J Yang. et al.. Resin modified MIL-53 (Fe) MOF for improvement of photocatalytic performance. Applied Catalysis B: Environmental, 2017, 203: 768–777 https://doi.org/10.1016/j.apcatb.2016.10.072
42	W Zhao, W Zhao, G Zhu. et al.. Black strontium titanate nanocrystals of enhanced solar absorption for photocatalysis. CrystEngComm, 2015, 17(39): 7528–7534 https://doi.org/10.1039/C5CE01263E
43	W Wang, X Chen, G Liu, et al. Monoclinic dibismuth tetraoxide: A new visible-light-driven photocatalyst for environmental remediation. Applied Catalysis B: Environmental, 2015, 176–177: 444–453 10.1016/j.apcatb.2015.04.026
44	J C Yu, J Yu, W Ho. et al.. Effects of F-doping on the photocatalytic activity and microstructures of nanocrystalline TiO2 powders. Chemistry of Materials, 2002, 14(9): 3808–3816 https://doi.org/10.1021/cm020027c
45	M Hasan, M Arshad, A Ali. et al.. Mg and La co-doped ZnNi spinel ferrites for low resistive applications. Materials Research Express, 2018, 6(1): 016302 https://doi.org/10.1088/2053-1591/aae3f6
46	V Cherepanov, T Aksenova, L Y Gavrilova. et al.. Structure, nonstoichiometry and thermal expansion of the NdBa(Co,Fe)2O5+δ layered perovskite. Solid State Ionics, 2011, 188(1): 53–57 https://doi.org/10.1016/j.ssi.2010.10.021
47	H Liu, J Yu. Catalytic performance of Cu-Ni/La0.75Sr0.25Cr0.5Mn0.5O3–δ for dry methane reforming. International Journal of Energy Research, 2022, 46(8): 10522–10534 https://doi.org/10.1002/er.7392
48	J H Kim, A Manthiram. LnBaCo2O5+δ oxides as cathodes for intermediate-temperature solid oxide fuel cells. Journal of the Electrochemical Society, 2008, 155(4): B385–B390 https://doi.org/10.1149/1.2839028
49	K Miyazaki, T Okanishi, H Muroyama. et al.. Development of Ni-Ba(Zr,Y)O3 cermet anodes for direct ammonia-fueled solid oxide fuel cells. Journal of Power Sources, 2017, 365: 148–154 https://doi.org/10.1016/j.jpowsour.2017.08.085
50	J Yang, T Akagi, T Okanishi. et al.. Catalytic influence of oxide component in Ni-based cermet anodes for ammonia-fueled solid oxide fuel cells. Fuel Cells, 2015, 15(2): 390–397 https://doi.org/10.1002/fuce.201400135
51	G Meng, C Jiang, J Ma. et al.. Comparative study on the performance of a SDC-based SOFC fueled by ammonia and hydrogen. Journal of Power Sources, 2007, 173(1): 189–193 https://doi.org/10.1016/j.jpowsour.2007.05.002
52	B Wang, T Li, F Gong. et al.. Ammonia as a green energy carrier: Electrochemical synthesis and direct ammonia fuel cell—A comprehensive review. Fuel Processing Technology, 2022, 235: 107380 https://doi.org/10.1016/j.fuproc.2022.107380
53	R K Sharma, M Burriel, L Dessemond. et al.. Design of interfaces in efficient Ln2NiO4+δ (Ln = La, Pr) cathodes for SOFC applications. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2016, 4(32): 12451–12462 https://doi.org/10.1039/C6TA04845E
54	Q A Huang, R Hui, B Wang. et al.. A review of AC impedance modeling and validation in SOFC diagnosis. Electrochimica Acta, 2007, 52(28): 8144–8164 https://doi.org/10.1016/j.electacta.2007.05.071
55	L Bian, C Duan, L Wang. et al.. Electrochemical performance and stability of La0.5Sr0.5Fe0.9Nb0.1O3–δ symmetric electrode for solid oxide fuel cells. Journal of Power Sources, 2018, 399: 398–405 https://doi.org/10.1016/j.jpowsour.2018.07.119

[1]

FEP-24020-OF-YS_suppl_1

Download

Viewed

Full text

Abstract

Cited

Shared

Discussed