Abstract
In this work, the nanostructural changes in a Ni/NiO cermet material, during its reduction and oxidation at 600 °C have been studied. A series of the NiO ceramic specimens (mode 1) were undergone to the next three treatment modes at 600 °C, namely: (2) one-time reduction in hydrogen of 99.99 vol% H2 purity; (3) one-time reduction in Ar–5 vol% H2 mixture; (4) redox cycling (5 cycles), each redox cycle comprises the stages of isothermal holding in Ar–5 vol% H2 mixture and in air, with intermediate stages of degassing. Increased porosity, along with an increased amount of reduced Ni, has been revealed in specimens after mode 2 test. In contrast to treatment in pure hydrogen, no substantial volume changes in the material after mode 3 test were found, and single micropores were detected only at the sites of contact of nickel phase particles. In contrast to modes 2 and 3, the following structural peculiarities in the course of redox cycling of as-sintered NiO ceramics (mode 4) were detected: (1) formation of a network of nanopores in the outer layer of a Ni-phase particle; (2) reduction of Ni-phase particle size by separating thin pieces of reduced Ni subgrains; (3) coagulation of fine Ni pieces that allows the porosity to be partially decreased and “bridges” to be formed; (4) clustering of the initial Ni-phase particles with the formation of nanopores at the sites of former boundaries; (5) formation of a network of reduced Ni that consists of Ni fringes and “bridges” and improves electrical conductivity and structural strength of the cermet.
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References
Atkinson A (1985) Transport processes during the growth of oxide films at elevated temperature. Rev Mod Phys 57:437–470
Clemmer RMC, Corbin SF (2009) The influence of pore and Ni morphology on the electrical conductivity of porous Ni/YSZ composite anodes for use in solid oxide fuel cell applications. Solid State Ionics 180:721–730
Ettler M, Blaβ G, Menzler NH (2007) Characterization of Ni–YSZ-cermets with respect to redox stability. Fuel Cells 5:349–355
Faes A, Hessler-Wyser A, Zryd A et al (2012) A review of RedOx cycling of solid oxide fuel cells anode. Membranes 2(3):585–664. https://doi.org/10.3390/membranes2030585
Faes A, Nakajo A, Hessler-Wyser A et al (2009) Redox study of anode-supported solid oxide fuel cell. J Power Sources 193:55–64
Gmelin L (1968) Gmelin handbook of inorganic chemistry, 8th edn. Springer, Berlin
Karmhag R, Niklasson GA, Nygren M (1999a) Oxidation kinetics of large nickel particles. J Mater Res 14:3051–3058
Karmhag R, Niklasson GA, Nygren M (1999b) Oxidation kinetics of small nickel particles. J Appl Phys 85:1186–1191
Karmhag R, Niklasson GA, Nygren M (2001) Oxidation kinetics of nickel nanoparticles. J Appl Phys 89:3012–3017
Peraldi R, Monceau D, Pieraggi B (2002) Correlations between growth kinetics and microstructure for scales formed by high-temperature oxidation of pure nickel. I Morphologies and microstructures. Oxid Met 58:249–273
Podhurska V, Vasyliv B (2012) Influence of NiO reduction on microstructure and properties of porous Ni–ZrO2 substrates. In: Proceedings of the 3rd international conference on oxide materials for electronic engineering (OMEE-2012). Lviv, 3–7 Sep 2012, pp 293–294
Podhurska V, Vasyliv B, Ostash O et al (2016) Influence of treatment temperature on microstructure and properties of YSZ–NiO anode materials. Nanoscale Res Lett 11:93. https://doi.org/10.1186/s11671-016-1306-z
Podhurska VY, Vasyliv BD, Ostash OP et al (2014) Structural transformations in the NiO-containing anode of ceramic fuel cells in the course of its reduction and oxidation. Mater Sci 49(6):805–811
Radovic M, Lara-Curzio E (2004) Mechanical properties of tape cast nickel-based anode materials for solid oxide fuel cells before and after reduction in hydrogen. Acta Mater 52:5747–5756
Railsback JG, Johnston-Peck AC, Wang J et al (2010) Size-dependent nanoscale kirkendall effect during the oxidation of nickel nanoparticles. ACS Nano 4:1913–1920
Simwonis D, Tietz F, Stoever D (2000) Nickel coarsening in annealed Ni/8YSZ anode substrates for solid oxide fuel cells. Solid State Ionics 132:241–251
Steele BCH, Heinzel A (2001) Materials for fuel-cell technologies. Nature 414:345–352
Thydén K (2008) Microstructural degradation of Ni–YSZ anodes for solid oxide fuel cells. Ph.D. Thesis, Technical University of Denmark, Roskilde, Denmark
Van der Pauw LJ (1958) A method of measuring specific resistivity and Hall effect of discs of arbitrary shape. Philips Res Rep 13:1–9
Van Herle J, Larrain D, Autissier N et al (2005) Modeling and experimental validation of solid oxide fuel cell materials and stacks. J Eur Ceram Soc 25:2627–2632
Vassen R, Simwonis D, Stoever D (2001) Modelling of the agglomeration of Ni-particles in anodes of solid oxide fuel cells. J Mater Sci 36:147–151
Vasyliv BD (2009) A procedure for the investigation of mechanical and physical properties of ceramics under the conditions of biaxial bending of a disk specimen according to the ring–ring scheme. Mater Sci 45(4):571–575
Vasyliv BD (2010) Improvement of the electric conductivity of the material of anode in a fuel cell by the cyclic redox thermal treatment. Mater Sci 46(2):260–264
Vasyliv BD, Podhurs’ka VY, Ostash OP et al (2013a) Influence of reducing and oxidizing media on the physicomechanical properties of ScCeSZ–NiO and YSZ–NiO ceramics. Mater Sci 49(2):135–144
Vasyliv BD, Ostash OP, Podhurska VY et al (2013b) Method of treatment of NiO-containing anodes for a solid oxide fuel cell (in Ukrainian). Patent of Ukraine No. 78992. Published on 10.04.13, Bulletin No. 7
Vasyliv B, Podhurska V, Ostash O (2017) Preconditioning of the YSZ-NiO fuel cell anode in hydrogenous atmospheres containing water vapor. Nanoscale Res Lett 12:265. https://doi.org/10.1186/s11671-017-2038-4
Waldbillig D, Wood A, Ivey DG (2005) Electrochemical and microstructural characterization of the redox tolerance of solid oxide fuel cell anodes. J Power Sources 145:206–215
Wang Y, Walter ME, Sabolsky K et al (2006) Effects of powder sizes and reduction parameters on the strength of Ni–YSZ anodes. Solid State Ionics 177:1517–1527
Wood A, Waldbillig D (2011) Preconditioning treatment to enhance redox tolerance of solid oxide fuel cells. US Patent 8,029,946 B2, 4 Oct 2011
Wuillemin Z, Autissier N, Luong M-T et al (2005) Modeling and study of the influence of sealing on a solid oxide fuel cell. In: Proceedings of the 1st european fuel cell technology and applications conference. Rome, 14–16 Dec 2005, pp 130–136
Yu JH, Park GW, Lee S et al (2007) Microstructural effects on the electrical and mechanical properties of Ni–YSZ cermet for SOFC anode. J Power Sources 163:926–932
Zhang Y, Liu B, Tu B et al (2009) Understanding of redox behavior of Ni–YSZ cermets. Solid State Ionics 180:1580–1586
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Kharchenko, Y., Blikharskyy, Z., Vira, V. et al. Study of nanostructural changes in a Ni-containing cermet material during reduction and oxidation at 600 °C. Appl Nanosci 10, 4535–4543 (2020). https://doi.org/10.1007/s13204-020-01391-1
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DOI: https://doi.org/10.1007/s13204-020-01391-1