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  • Kinoshita, Masahiro  (10)
  • 1
    In: ECS Transactions, The Electrochemical Society, Vol. 64, No. 2 ( 2014-08-14), p. 225-232
    Abstract: Ni-yttria stabilized zirconia (YSZ) cermet is evaluated as anode material for the solid oxide fuel cells operated by the direct internal steam reforming of iso-octane. Effect of the cell temperature and the steam/carbon ratio in the fuel was examined from the point of view of the cracking reaction performance, identification of the elementary process which governs power generation and durability. When both steam/carbon ratio and cell temperature are high enough, iso-octane is cracked to generate H 2 and CO. The cracking reaction of iso-octane on the surface of the Ni-YSZ anode governs the reaction rate of the anode electrode. Outlet gas composition from the cell was analyzed by gas chromatography, and the single cell property was measured by the electrochemical method.
    Type of Medium: Online Resource
    ISSN: 1938-5862 , 1938-6737
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2014
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  • 2
    In: ECS Transactions, The Electrochemical Society, Vol. 68, No. 1 ( 2015-06-02), p. 2831-2843
    Abstract: A porous cermet of Ni and yttria stabilized zirconia (Ni-YSZ) cermet was used as an anode electrode for the octane-direct use SOFC. Influences of operating conditions, steam/carbon ratio and cell temperature on the steam internal reforming reaction and electrochemical reaction on the anode electrode were investigated. In order to understand the influence of difference in branching of carbon chain, n-octane (linear alkane) and iso-octane (branched chain alkane) were used. By the internal steam reforming of n-octane, H 2 , CO, CO 2 , CH 4 , and C 2 H 6 are generated. The reforming rate of n-octane is large, while the reforming of iso-octane is slow reaction. When the fuel utilization is low, H 2 and CO preferentially contribute for the power generation. The carbon deposition rate is quite large, although the initial power generation performance is high. Especially, the carbon deposition is remarkable when iso-octane is used as the fuel.
    Type of Medium: Online Resource
    ISSN: 1938-5862 , 1938-6737
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2015
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  • 3
    Online Resource
    Online Resource
    The Electrochemical Society ; 2015
    In:  Journal of The Electrochemical Society Vol. 162, No. 10 ( 2015), p. F1107-F1113
    In: Journal of The Electrochemical Society, The Electrochemical Society, Vol. 162, No. 10 ( 2015), p. F1107-F1113
    Type of Medium: Online Resource
    ISSN: 0013-4651 , 1945-7111
    RVK:
    Language: English
    Publisher: The Electrochemical Society
    Publication Date: 2015
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  • 4
    Online Resource
    Online Resource
    The Electrochemical Society ; 2015
    In:  ECS Meeting Abstracts Vol. MA2015-03, No. 1 ( 2015-07-15), p. 173-173
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2015-03, No. 1 ( 2015-07-15), p. 173-173
    Abstract: 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 o C 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 o C. The cell temperature range was 700-950 o C. 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, H 2 , CO, CO 2 , and CH 4 is mainly produced. When the iso-octane is used as the fuel, small amount of C 2 H 6 is also generated in addition to them. Only H 2 and CO contribute to the power generation directly. Rate-determining process of the electrode reaction is a cracking reaction to H 2 and CO.
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2015
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  • 5
    In: ECS Transactions, The Electrochemical Society, Vol. 68, No. 1 ( 2015-06-02), p. 1391-1401
    Abstract: The possibility of performance recovery of the sulfurated Ni-yttria stabilized zirconia anode electrode by shifting the anode electrode potential to the stable region, in which nickel exists as metal, is investigated. The effect of controlling the potential of the anode electrode to the stable region to suppress the generation of nickel sulfide is also revealed. The surface of Ni particle reacts with sulfur to form Ni 3 S 2 in a low temperature region; however, the nickel is reduced to metallic by shifting the electrode potential to –1.9 V vs reference electrode exposed to O 2 – When the potential of the Ni-based anode electrode is maintained at the value of ≤ -1.9 V vs the reference electrode potential, the sulfidation of nickel is inhibited.
    Type of Medium: Online Resource
    ISSN: 1938-5862 , 1938-6737
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2015
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  • 6
    Online Resource
    Online Resource
    The Electrochemical Society ; 2015
    In:  ECS Meeting Abstracts Vol. MA2015-03, No. 1 ( 2015-07-15), p. 172-172
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2015-03, No. 1 ( 2015-07-15), p. 172-172
    Abstract: A small and high-performance solid oxide fuel cell (SOFC) system is promising as a power source for many potential mobile robot applications. To realize the small SOFC system, the direct use of liquid hydrocarbon fuel, which has high energy density and is easy to storage and carry, is desirable. The optimization of type of fuel, operating conditions, and a fuel electrode (anode electrode) is essential. In the view point of the use at high temperatures in summer outdoor, octane having high boiling temperature is a good candidate as the fuel. Steam reforming is the first choice for the internal reforming method because it has been frequently-studied for the direct use of methane fuel. A porous cermet of Ni and yttria-stabilized zirconia (YSZ), which has widely been studied as an anode electrode for the internal reforming operation SOFC, is one of promising anode electrode materials, however, performance degradation due to sulfur poisoning and carbon deposition on the anode electrodes surface is concerned. A porous cermet of Cu and gadolinium oxide-doped ceria (Cu-GDC), which, respectively, have excellent sulfur tolerance and oxygen ion supply property, has high potential for the anode electrode of SOFC operated by internal reforming of methane. Therefore, in this study, the Cu-GDC cermet was focused as an alternative anode electrode for the octane-direct use SOFC. The aim of this study is to clarify the effects of operating conditions on the reforming reaction and electrochemical reaction on the Cu-GDC cermet anode electrode. In this study, the fuel-cracking reaction, which occurs at elevated temperature in the presence of excess steam, was estimated. In order to understand the effect of difference in branching of carbon chain, n-octane (linear alkane) and iso-octane (branched chain alkane) were used. Octane and steam were supplied to the SOFC cell by bubbling carrier gas (He or Ar) at a constant rate. Temperature of the octane bubbler and the carrier gas flow rate was 30 o C 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 a S/C ratio from 0.5 to 5.5 by changing the temperature of the water bubbler from 30 to 80 o C. The cell temperature range was 700-850 o C. I-V and I-P characteristics, and stable power generation property by constant current were investigated to demonstrate the octane direct internal reforming operation of SOFC. The effects of S/C ratio and cell temperature on the open circuit voltage (OCV) and I-V and I-P characteristics were investigated. In order to identify the chemicals generated by the fuel cracking reaction, outlet gas compositions from the cell of open circuit condition and power generation condition were analyzed by gas chromatography. The following are the main findings that we have revealed in the present study. By raising the S/C ratio and/or the cell temperature, the reforming reaction is facilitated, but fluctuation of the OCV is increased. Chemical species and their ratio generated by the cracking reaction are changed by the difference in the carbon-chain of octane. Mainly H 2 , CO, CO 2 , CH 4 , and C 2 H 6 are generated in the reforming reaction of n-octane, and C 3 H 8 , CH 3 OH, and C 4 H 10 are also generated in addition to those in the reforming reaction of iso-octane. However, the main electrode reaction to generate electrical power is only the electrochemical oxidation of H 2 and/or CO. By using the n-octane fuel, the carbon deposition is reduced. The rate-determining process is dissociation to H and CO.
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2015
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  • 7
    Online Resource
    Online Resource
    The Electrochemical Society ; 2014
    In:  ECS Meeting Abstracts Vol. MA2014-02, No. 20 ( 2014-08-05), p. 1002-1002
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2014-02, No. 20 ( 2014-08-05), p. 1002-1002
    Abstract: Introduction For many potential mobile robot applications, current power supply technology (such as the lithium ion battery technology) is in fact a key limiting factor due to its low energy density. Solid oxide fuel cells (SOFCs) are a promising alternative and can overcome limitations of current battery technology. This is because SOFCs can use not only hydrogen but also hydrocarbon fuels which have high energy density such as gasoline and so on. However, hydrocarbon is broken down into hydrogen and carbon at a high temperature and carbon precipitate on anodes. The rate of carbon deposition for the nikkel-gadolinia doped ceria (Ni-GDC) was slower than that for the nikkel-yttria stabilized zirconi (Ni-YSZ). Ceria can be reduced from Ce 4+ to Ce 3+ , which causes the suppression of carbon deposition on the carbon deposition on the Ni-GDC anode 1) . Moreover, cupper based cermets anode is stable in hydrocarbon environments 2) . Therefore, we paid attention to Cu-GDC cermet anode. The objective of this research is to demonstrate octane direct introduction generation of SOFCs using Cu-GDC anode. Experimental Surface-polished YSZ pellets of 2 mm in thickness were used for the electrolyte. Pt cathode electrode and Pt reference electrode were prepared on the surface and side of the pellets, respectively, by firing Pt paste at 1300 o C for 1 h. Then, a commercially available CuO powder and GDC powder (CuO/GDC=55/45 (wt)) were thoroughly mixed in a vacuum using the planetary ball mill (LP-1, Ito Seisakusho Co., Ltd., 200 rpm, 24 h), and made into CuO-GDC pastes using ethyl-cellulose and organic solvent. The CuO-GDC paste was screen-printed in diameter of 8mm on the YSZ pellets and sintered at 900 o C for 1 h. Octane and steam were supplied to the SOFC cell by bubbling carrier gas (He) at a constant rate. Octane bubbler temperature was 30 o C, and Steam/Carbon ratio (S/C) were controlled by changing the temperature of the water bubbler from 30 to 70 o C. Electrochemical property was measured over a temperature range of 800-700 o C. During the constant current generation, exhaust gas was analyzed by gas chromatography. Results Figure 1 shows current-voltage ( I - V ) and current-power ( I - P ) characteristics for the cells at 750 o C. Octane-direct introduction generation is possible in SOFCs by using the Cu-GDC anode. A power generation characteristic improves gradually with the rise of S/C. For the lower S/C, the I - V curves are highly nonlinear, while the I - V curve for S/C=8.86 is essentially linear. Figure 2 shows impedance spectra for the cells with the Cu-GDC anode at 750 o C under open circuit conditions. The ohmic resistances that we associate with the electrolyte are obtained from the high-frequency intercept of the arc with the real axis, are the same and small values, while the total impedance from the low-frequency intercept in the arc with the real axis is increased with the S/C. The difference between the total impedance and electrolyte impedance is the anode electrode impedance. Therefore, the dominant factor of a power generation characteristic is anode electrode resistance. References 1) Hirofumi Sumi, Toshiaki Yamaguchi, Koichi Hamamoto et al. , “Impact of direct butane microtubular solid oxide fuel cells” J. Power Sources, 220 (2012) 74-78 2) R.J. Gorte, H. Kim, J.M. Vohs, “Novel SOFC anodes for the direct electrochemical oxidation of hydrocarbon” J. Power Sources, 106 (2002) 10-15.
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2014
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  • 8
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2014-02, No. 20 ( 2014-08-05), p. 1000-1000
    Abstract: Introduction For many potential mobile robot applications, current power supply technology (such as the lithium ion battery technology) is in fact a key limiting factor due to its low energy density. Solid oxide fuel cells (SOFCs) are a promising alternative and can overcome limitations of current battery technology. This is because SOFCs can, in principle, use not only hydrogen but also hydrocarbon fuels which have high energy density such as gasoline and so on. Ni-YSZ cermet is the most promising anode material for SOFCs because of its low cost, chemical stability, and closely matched thermalexpansion coefficients with the dense YSZ electrolyte. Ni is an excellent catalyst for hydrocarbon fuel reforming and cracking, which leads to rapid carbon deposition inside the SOFC anode and causes coking and deactivation 1) . In principle, the carbon deposition on Ni can be depressed by adding steam in the hydrocarbon fuel 2,3) , whereas few detailed investigations of SOFCs that operate on gasoline fuel have been reported. In this work, we studied the effect of steam content and demonstrated the direct operation of SOFCs by octane which is a main ingredient of gasoline. In the case of the Ni-YSZ anode, the operation temperature must be high in order to avoid sulfur poisoning 4 -6 ) , because most commercially available fuels contain sulfur. Therefore, in this study, the SOFCs operation was conducted at high temperature of 950 o C. Experimental Surface-polished YSZ pellets of 2 mm in thickness were used for the electrolyte. Pt cathode electrode and Pt reference electrode were prepared on the surface and side of the pellets, respectively, by firing Pt paste at 1300 o C. Then, NiO powder and GDC powder (NiO/YSZ=6/4 (wt)) were thoroughly mixed in a vacuum using the planetary ball mill (200 rpm, 12 h), and made into NiO-YSZ pastes using ethyl-cellulose and organic solvent. The NiO-YSZ paste was screen-printed in diameter of 8 mm on the YSZ pellets and sintered at 1200 o C for 1 h. Octane and steam were supplied to the SOFC cell by bubbling carrier gas (He) at a constant rate. Octane bubbler temperature was 30 o C, and Steam/Carbon ratio (S/C) were controlled by changing the temperature of the water bubbler from 40 to 70 o C. Electrochemical properties (open circuit voltage, anode electrode resistance, I - V and I - P characteristics, stable power generation property) were measured over a temperature range of 950-700 o C. During the constant current generation, exhaust gas was analyzed by gas chromatography. Results and Discussion Figure 1 shows I - V and I - P characteristics for the cells at 950 o C in wet octane. Maximum power density of 35 mW/cm 2 was obtained by S/C of 8.9. The power density decreased with S/C quickly. Figure 2 shows the time course of cell voltage at a drawn current density of 5.2 mA/cm 2 for S/C of 3.5. The cell voltage was stable. That is, carbon deposit does not arise even in the cell of the Ni-YSZ anode in low S/C of 3.5 when the operation temperature is high of 950 o C. References 1) S. Mclntosh and R.J. Gorte, “Direct Hydrocarbon Solid Oxide Fuel Cells,” Chemical Reviews , 104 (2004) 4845- 4865. 2) K. Sasaki and Y. Teraoka, “Equilibria in Fuel Cell Gases: I. Equilibrium Compositions and Reforming Conditions,” Journal of Electrochemical Society , 850 (7) (2003) A878-A884. 3) K. Sasaki and Y. Teraoka, “Equilibria in Fuel Cell Gases: II. The C-H-O Ternary Diagrams,” Journal of Electrochemical Society , 850 (7) (2003) A885-A888. 4) K. Sasaki, K. Susuki, A. Iyoshi, M. Uchimura, N. Imamura, H. Kusaba, Y. Teraoka, H. Fuchino, K. Tsujimoto, Y. Uchida, N. Jingo, “H 2 S Poisoning of Solid Oxide Fuel Cells,” J. Electrochem. Soc. , 153 (2006) A2023–A2029. 5) P. Lohsoontorn, D.J.L. Brett, N.P. Brandon, “Thermodynamic predictions of the impact of fuel composition on the propensity of sulphur to interact with Ni and ceria-based anodes for solid oxide fuel cells,” Journal of Power Sources , 175 (2008) 60–67. 6) H. Kishimoto, Y-P Xiong, K. Yamaji, T. Horita, N. Sakai, M.E. Brito, H. Yokokawa, “Stability of Ni base anode for direct hydrocarbon SOFCs, ” Journal Chemical Engineering of Japan , 40 (13) (2007) 1178-1182.
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2014
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  • 9
    Online Resource
    Online Resource
    The Electrochemical Society ; 2015
    In:  ECS Transactions Vol. 68, No. 1 ( 2015-06-02), p. 2819-2829
    In: ECS Transactions, The Electrochemical Society, Vol. 68, No. 1 ( 2015-06-02), p. 2819-2829
    Abstract: A porous cermet of Cu and gadolinium oxide-doped ceria (Cu-GDC), which, respectively, have excellent sulfur tolerance and oxygen ion supply property, was focused as an anode electrode for the octane-direct use SOFC. Influences of operating conditions, steam/carbon ratio and cell temperature, on the steam internal reforming reaction and electrochemical reaction on the Cu-GDC cermet anode electrode were investigated. In order to understand the influence of difference in branching of carbon chain, n-octane (linear alkane) and iso-octane (branched chain alkane) were used. By raising the S/C ratio, the carbon deposition is decreased but the fluctuation range of the OCV is increased. Mainly H 2 , CO, CO 2 , CH 4 , and C 2 H 6 are generated in the reforming reaction of n-octane, and C 3 H 8 , CH 3 OH, and C 4 H 10 are also generated in addition to those in the reforming reaction of iso-octane. By using the n-octane fuel, the carbon deposition is reduced. The rate-determining process is dissociation to H 2 and CO.
    Type of Medium: Online Resource
    ISSN: 1938-5862 , 1938-6737
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2015
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  • 10
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2015-03, No. 1 ( 2015-07-15), p. 180-180
    Abstract: A small and high-performance solid oxide fuel cell (SOFC) system has a potential as a power source for mobile use like automobile. To realize the small SOFC system, the direct use of liquid hydrocarbon fuel, which has high energy density and is easy to storage and supply, is desirable. In order to use the existing fuel supply infrastructure, the SOFC should be operated by gasoline. Gasoline sold in Japan contains H 2 S up to 10ppm. Thus, automotive SOFC must be able to be stably operated at 10ppm H 2 S-containing gasoline. A porous cermet of Ni and yttria-stabilized zirconia (YSZ), which has widely been studied as an anode electrode for the internal reforming operation SOFC, is one of promising anode electrode materials; however, performance degradation of anode electrode due to sulfur poisoning occurs by the impurity in the gasoline. Principal sulfur poisoning reaction is sulfide generation of Ni in the middle and low temperature region where the anode electrode is exposed at starting and stopping of the SOFC. In this study, the effect of controlling the potential of the anode electrode to the stable region on the suppressing the generation of nickel sulfide is revealed. The possibility of performance recovery of the sulfurated anode by shifting the anode electrode potential to the stable region is also investigated. First of all, three kinds of reactions of H 2 +0.5O 2 =H 2 O, H 2 S=H 2 +0.5S 2 , and S 2 +1.5Ni=Ni 3 S 2 are assumed to occur on the anode electrode and the stable electrode potential region for the various cell temperatures was theoretically estimated by using the Gibbs energy of the reactions calculated by the thermodynamic database MALT2. Then, experimental studies were conducted by using Ni model electrodes and Ni-YSZ cermet electrodes. Microstructure change of the electrode was analyzed by scanning electron microscopy and electron probe microanalysis. Electrode performances were investigated by electrochemical analysis (current-voltage measurement and ac-impedance method). The reduction of the sulfurated nickel electrode generated at 400 o C in 10ppm- H 2 S containing hydrogen fuel to metallic Ni by shifting the electrode potential was investigated. Independently of open circuit voltage state or power generation state, all of the Ni surface and the Ni/YSZ interface formed a sulfur compound. When the electrode potential was shifted to -1.9 V vs reference electrode, the reduction reaction was preceded. Although the reduction rate decreases with decreasing the applied potential, in the range of more than -1.9 V it was independent of the applied potential. The decreased performance of the anode electrode by sulfurization of nickel was recovered by controlling the electrode potential. Although it takes a long time to reduce when the Ni particles is poisoned to the inside, it was recovered in a short period of time when the only the surface of Ni is poisoned. Effect of the holding the electrode potential in the stable region for the inhibition of the generation reaction of nickel sulfide was investigated. When the electrode potential was kept at -1.9 V vs reference electrode, the Ni-electrode was maintained the metal state even in the 10ppm-H 2 S/H 2 atmosphere at 400 o C.
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2015
    detail.hit.zdb_id: 2438749-6
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