Cracking Reaction of Octane Fuel and Electrochemical Reaction on Ni-YSZ Cermet Anode of Internal Steam Reforming Solid Oxide Fuel Cell
Authors: Kinoshita Masahiro , Tomomichi Keita , Yamagami Shun , Yamada Yuki , Terai Takayuki , Sasaki Kazuya 
Published: February 2020

Solid oxide fuel cell (SOFC) can, in principle, use not only hydrogen but also hydrocarbon fuels which have high energy density. Then, SOFC is a promising power source for many potential mobile robot applications. Octane is a good candidate as fuel due to high boiling point enough to be in the liquid phase even at high temperatures in summer. Performance of the internal reforming SOFC is governed by anode electrode material, internal reforming method, and operating conditions. Ni-yttria stabilized zirconia (Ni-YSZ) cermet is the most promising anode material for SOFC because of its low cost, chemical stability, and closely matched thermal expansion coefficients with the dense YSZ electrolyte. Steam reforming is the first choice for the internal reforming method because it has been frequently-studied for the direct use of methane fuel. Then, operation of SOFC by internal steam reforming of octane has been studied. However, cracking reactions on the YSZ anode, which is affected by the operating conditions, have not been elucidated sufficiently.

The purpose of this study is to clarify the cracking reaction of octane fuel and the electrochemical reaction of the Ni-YSZ anode electrode under various operating conditions. In this study, the fuel-cracking reaction on the Ni-YSZ anode electrode is estimated by gas chromatography with thermal conductivity detector. Anode electrode performance is studied by electrochemical measurement. Two types of octane (n-octane; linear alkane, iso-octane; branched chain alkane) are used in order to elucidate the effect of difference in carbon-chain structure. Octane and steam of equilibrium vapor pressure were supplied to the SOFC cell by bubbling carrier gas (He) at a constant rate. Temperature of the octane bubbler and the carrier gas flow rate was 30 oC and 10 ml/min, respectively. The carrier gas flow rate of the water bubbler was 83 ml/min. Steam/carbon ratio (S/C) was controlled over an S/C ratio from 0.5 to 5.5 by changing the temperature of the water bubbler from 30 to 80 oC. The cell temperature range was 700-950 oC.

The octane internal steam reforming operation of SOFC was demonstrated by I-V and I-P characteristics and stable power generation property by constant current. The effects of operating conditions (S/C ratio and cell temperature) on the open circuit voltage (OCV) and power generation property were investigated. The chemicals generated by the cracking reaction of octane at various operating conditions were analyzed by gas chromatography and compared. The difference in outlet gas compositions from the cell of open circuit condition and power generation condition revealed the main species consumed for the power generation reaction on the anode electrode. The electrochemical reaction resistance of the Ni-YSZ anode was measured by ac impedance method and the rate-determining process was identified.

In this study the following was revealed. When the S/C and/or the operating temperature are high, the reforming reaction rate is large. By the reforming reaction of n-octane, H2, CO, CO2, and CH4 is mainly produced. When the iso-octane is used as the fuel, small amount of C2H6 is also generated in addition to them. Only H2 and CO contribute to the power generation directly. Rate-determining process of the electrode reaction is a cracking reaction to H2 and CO.