Fuel 88 (2009) 19701974

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Copperterbia and coppergadolina anodes for direct hydrocarbon solid oxide fuel cells: A fundamental comparison of their physicochemical features and performances
Luis F. DElia Camacho *, Jorge A. Moncada Vivas
Petrleos de Venezuela (PDVSA)-Intevep, Gerencia General de Renacin e Industrializacin, Gerencia Tcnica de Renacin, Apartado 76343, Caracas 1070-A, Venezuela

a r t i c l e

i n f o

a b s t r a c t
Copperterbia and coppergadolina supported electrolyte SOFCs have been prepared by using standard procedures; such as, tape casting, dual tape casting, painting and impregnation. Anode XRD patterns analysis lead to the following chemical formulas: TbO1.823CuOZr0.8Y0.2O1.9 and Gd2O3CuO Zr0.8Y0.2O1.9. Since TPR proles and cell performances are fundamentally based on solid state RedOx reactions, a comparative analysis could suggest that there is an apparent correlation between them. This rst approach may be considered as the basis of a simple methodology to predict SOFC anodes performances. CuTbO2 SOFC performance depends on the hydrocarbon nature (toluene < n-heptane < cyclohexane < 1hexene), the cell behaviour (in term of power density) is improved when light hydrocarbons (those which have low carbon/hydrogen ratio content) are fed. Furthermore, the performance is improved by successive anode reactivations using hydrogen. 2009 Elsevier Ltd. All rights reserved.

Article history: Received 10 December 2008 Received in revised form 5 March 2009 Accepted 16 March 2009 Available online 5 April 2009 Keywords: SOFC anodes Terbia Gadolina Hydrocarbons

1. Introduction Although the Bolivarian Republic of Venezuela is one of the most important oil producers, hydrogen and fuel cells R&D activities have strongly been promoted. Based on hydrocarbon existing infrastructure, the aim is to look for opportunities that employ environmentally friendly and efcient energy supply devices; such as, direct hydrocarbon solid oxide fuel cells (SOFC). SOFC are systems that offer some advantages: (i) high electric conversion efciency; (ii) cogeneration-combined heat and power generation (CHP); (iii) fuel exibility; (iv) size and sitting exibility and (vi) transportation-stationary applications [1]. Direct hydrocarbon oxidation SOFC application was shown by Gorte and co-workers [2]; thereafter, other related developments have also been reported [312]. Most of the cited studies are focused on novel sulphurcarbon tolerant anodes, since it could be the major aspect to be dominant when hydrocarbons are transformed in SOFC. Table 1 summarises the state of the art on direct hydrocarbon SOFC anodes composition. In the face of the state of the art, new chemical and mechanical stable anode developments are still topics of interest. Based on pure catalytic properties, lanthanides could be considered as potential candidates for direct hydrocarbon SOFC anodes [1113]. Nevertheless, these chemical elements have not been evaluated in SOFC devices yet. The aim

of this article is to address copperterbia and coppergadolina anodes supported electrolyte SOFC properties, establishing their physicochemical properties and performances when hydrogen, toluene, n-heptane, 1-hexene and cyclohexane are used as fuels. 2. Experimental 2.1. Cell fabrication Based on the procedures detailed elsewhere for copperceria anode fabrication [14], SOFC components were prepared. Some highlights are given: (i) Yttria Stabilised Zirconia (YSZ) electrolyte were prepared by tape casting using YSZ (TOSOH-Zirconia TZ-8Y), Duramax D-3005 (dispersant), Duramax B-1000 (binder) and Duramax HA-12 (plasticiser). (ii) The anode support was fabricated by dual tape casting using same components used in (i). Additionally, poly(methyl methacrylate) (Expotech) and graphite powder (Alfa Easer, 99.995%) were employed as pore formers. Once electrolyte and anode support were prepared, they were sintered at 1550 C. (iii) Strontium-doped Lanthanum Manganite (LSMYSZ) cathode was prepared by painting, with a LSMYSZglycerine mixture, the non-porous surface of a YSZ disc (0.72 cm2). After painting, components were sintered at 1250 C.

* Corresponding author. Tel.: +58 212 3307134; fax: +58 212 3307230. E-mail addresses: delialf@pdvsa.com, deliaclf@cantv.net (L.F. DElia Camacho). 0016-2361/$ - see front matter 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2009.03.019

L.F. DElia Camacho, J.A. Moncada Vivas / Fuel 88 (2009) 19701974 Table 1 State of the art on anode composition for direct hydrocarbon SOFC. Metals Transition metals Nickel [4] Cobalt [10] Molybdenum [13] Zirconium [13] Ceria [2] Europia, terbia, praseodymia, gadolina, samaria and lanthana [1113] Remarks High electrocatalytic activity. Deactivation by high carbon deposition rates

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Lanthanides

High electrocatalytic activity. Deactivation by high carbon deposition rates Medium electrocatalytic activity. Low power generation since partial hydrocarbon oxidation is favoured vs. CO2 production Medium catalytic activity, not tested in SOFC Very high catalyst activity, electric insulating Medium catalytic activity, not tested in SOFC

(iv) The porous side of the YSZ electrolyte (anode support) was impregnated with metallic precursors: (a) 10 wt% terbium

or gadolinium aqueous solution (from Tb(NO3)3 5H2O (99.9%, Aldrich) or Gd(NO3)3 6H2O (99.99%, Aldrich)) was spread out on the porous YSZ anode support and sintered at 450 C and (b) 20 wt% copper aqueous solution (from Cu(NO3)2 2,5H2O (98%, Aldrich)) was also spread out on the porous YSZ anode support and sintered at 450 C. (v) The built cell was provided with platinum and gold cathodic and anodic current collectors respectively. The cell was stick to the top of an alumina tube employing Ceramabond 571-P and Ceramabond 571-L as a ceramic seals.

2.2. Anode physicochemical characterisation The porous YSZ anode support was characterised by Mercury Intrusion Porosimetry (MIP) using a Micromeritics AutoPore IV 9500 Series. Morphology and elemental analyses were performed using a scanning electron microscope coupled with an energy dispersive X-ray detector (SEM-EDX, JEOL JSM-6490). Crystallographic data were obtained by X-ray diffraction technique (XRD, PANalytical XPert PRO XRD system). Additionally, temperatureprogrammed reduction (TPR) proles were recorded at 5% H2/Ar, 20 ml min1 and 5 oC min1 by using a Micromeritics AutoChem model 2920.

Fig. 1. MIP prole of the porous YSZ anode support.

Fig. 2. EDX spectra of anode supported electrolyte SOFC: (a) CuTbO2 and (b) CuGd2O3.

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2.3. Cell operation The cell was heated or activated, with a hydrogen ow of 10 ml min1, using a tubular furnace (Lindberg/Blue M tubular furnace) at 700 C (2 C min1). Thereafter, hydrocarbons were pumped into the cell with a perfusor syringe pump (Cole-Palmer 74900 series) at 1.5 ml h1. Nitrogen (6 ml min1) was used as a carrier. 2.4. Evaluation of cells performance Cell performances were evaluated obtaining potentialcurrent density (Ej) and powercurrent density (Pj) curves in: hydrogen (H2), n-heptane (n-C7H16), toluene (C7H8), cyclohexane (C6H12) and 1-hexene (C6 H@ ). In some cases, products were monitored by on 12 line gas chromatographic mass spectrometry (GCMS) analysis using a GC (Agilent Technologies Model 6890N) and MS detector (Model 5973). Details on the experimental setup and cell assembling have been already published [14,15]. 3. Results and discussion 3.1. Anode physicochemical characterisation SEM images conrm that YSZ (electrolyte) is compact and dense; its thickness is about 60 lm. The MIP prole shown in

Fig. 1 clearly indicates the presence of two average pore sizes in the porous YSZ anode support: 2 and 11 lm. This bimodal pore size distribution is due to the use of graphite and polymethylmetacrylate as pore formers; as a result, high porosity for impregnation is guaranteed. EDX spectra (Fig. 2) indicate that anodes are only composed by the main elements; any other impurities from precursors and additives are thermally decomposed during preparation steps. Comparing the obtained XRD patterns (Fig. 3) with crystallographic database, it can be established that anode chemical formulas correspond to TbO1.823CuOZr0.8Y0.2O1.9, and Gd2O3CuOZr0.8Y0.2O1.9. For simplicity, anodes will be named as CuTbO2 (copperterbia), and CuGd2O3 (coppergadolina). In order to compare the obtained TPR curves, metal oxides (Gd2O3, TbO2 and CuO) were separately impregnated on YSZ anode support following the SOFC anodes preparation methodology. Metal oxide TPR proles provide notable information about metal oxides reducibility level. These remarkable aspects could be correlated to the anode TPR proles and SOFC electrochemical performances. It has to be noted that CuO shows the highest hydrogen consumption and the lowest reduction temperature (Fig. 4a), the inset zooms in the Gd2O3 and TbO2 hydrogen consumption region. TPR proles of CuTbO2 and CuGd2O3 anodes are shown in Fig. 4b, the reducibility (based on temperature reduction peaks) is established as: CuTbO2 > CuGd2O3.

Fig. 3. XRD spectra of anode supported electrolyte SOFC: (a) CuTbO2 and (b) Cu Gd2O3.

Fig. 4. TPR proles of: (a) metal oxides supported on YSZ and (b) anodes supported electrolyte SOFC.

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Comparing anode TPR proles with those recorded for pure metal oxides, two important aspects may be pointed out when: (i) reduction peaks are shifted to lower temperatures, thus materials are easier to reduce and (ii) reducibility order is changed: Gd2O3 > TbO2 vs. CuTbO2 > CuGd2O3. The fact of mixing Gd2O3 or TbO2 with CuO (main anode components) brings up slight TPR differences that could be due to a sort of synergy or chemical interaction between lanthanide oxides and copper. This synergy could impact cell performance since solid state RedOx reactions, those shown in TPR proles, are the main process taking place during SOFC operation. 3.2. Electrochemical performance of CuTbO2 and CuGd2O3 cells operated with H2 and C7H8 Ej and Pj cells proles for H2 and C7H8 (Fig. 5) follow the typical tendency for these devices [16]. The open circuit voltage (OCV) is closed to the value predicted by the Nernst equation for H2 (1.15 V); however, it is slightly minor for C7H8 (calculated assuming CO2 and H2O as products). It was found by GCMS that CO2 and H2O are not the unique products; some organic molecules produced by toluene thermochemical coupling were also detected. This is why the experimental OCV value for C7H8 differs from that predicted by Nernst equation. Fig. 6 shows the maximum cells power density obtained in both fuels. As it was expected the higher power density is achieved when C7H8 is used, which is due to the fact that it can transfer

more electrons per mol of fuel (complete oxidation to CO2: 2e/ H2 vs. 36e/C7H8). The power tendency follows the order Cu TbO2 > CuGd2O3, which is similar to the order found for the anodes in TPR tests. This apparent relation between SOFC performances and anode TPR proles could be the basis of a simple methodology to predict and correlate, as a rst approach, SOFC anodes behaviours. Further work has to be performed in order to evaluate the inuence of other parameters, thus a reliable mathematical correlation between anode reducibility level and power density could be set up. It has been reported that ceria is responsible for hydrocarbon oxidation, while copper provides electric conductivity in copper ceria SOFC [7]. However, TPR proles differences may suggest that lanthanide oxides (Gd2O3 or TbO2) could not be the only involved in hydrocarbon conversion reactions. The high CuO reducibility level or RedOx features could also indicate a copper dual effect in the reaction, since Gd2O3 and TbO2 reducibility are affected by the presence of copper species. Based on the well known CuOCu RedOx reversibility [17], under specic operation conditions, both copper species may promote similar effects on RedOx lanthanide oxides behaviour. 3.3. Electrochemical performance of CuTbO2 cell operated with n-C7H16, C6H12, C7H8 and C6 H@ 12 The maximum power density obtained for CuTbO2 SOFC was higher than that for CuGd2O3 SOFC. As a result, CuTbO2 SOFC performance was evaluated when the cell was operated with other hydrocarbons, Ej and Pj proles are shown in Fig. 7. Hydrogen reactivations where carried out before any hydrocarbon tests, Fig. 7a shows the proles obtained during the successive hydrogen reactivations (1H2, 2H2, 3H2, 4H2 or xH2 indicate the hydrogen order feeding into the cell just before each operation with hydrocarbons). In the same way, Fig. 7b shows the proles obtained for n-C7H16, C7H8, C6H12 and C6 H@ . In resume, fuels order feeding into 12 the cell is: 1H2, n-C7H16, 2H2, C7H8, 3H2, C6H12, 3H2, C6 H@ , 4H2. 12 According to Fig. 7a, hydrogen maximum power density values increase when the cell is successively operated with hydrocarbons (the power tendency is 1H2 < 2H2 < 3H2 < 4H2). It can also be noted that the decaying rates for Ej curves decrease with the consecutive hydrogen cell reactivation or operation; this could be explained considering that ohmic resistance cell factor may also decrease. Fig. 7b shows how the cell performance is inuenced by hydrocarbon chemical nature, maximum power density tendency order can be established as follows: C7H8 < n-

Fig. 5. SOFCs Ej and Pj proles: (a) H2 and (b) C7H8. (h) CuTbO2 and (4) Cu Gd2O3.

Fig. 6. Maximum power densities for CuTbO2 and CuGd2O3 SOFCs operated with H2 and C7H8.

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was about 60 lm. MIP prole clearly indicates the presence of two average pore sizes in the porous YSZ anode support: 2 and 11 lm. Anode XRD patterns analysis allow to propose the following chemical formulas: TbO1.823CuOZr0.8Y0.2O1.9 and Gd2O3 CuOZr0.8Y0.2O1.9. Metal oxide and anode TPR proles could be related to the SOFC electrochemical performance, since both are fundamentally based on solid RedOx reactions. The fact of mixing Gd2O3 or TbO2 with CuO (main anode components) brings up slight TPR prole differences that could be due to a sort of synergy between lanthanide oxides and copper species. TPR curves may suggest that not only Gd2O3 or TbO2 could be involved in the hydrocarbon conversion; the high CuO reducibility level could indicate a dual role in the electrocatalytic reactions. In other words, copper species may also be involved on RedOx SOFC reactions. Maximum power density tendency follows the order: CuTbO2 > CuGd2O3 and it is similar to the order found for the anodes reduction in TPR tests. This apparent relation between SOFC performances and anode TPR features could be the basis of a simple methodology to predict and correlate, as a rst approach, SOFC anodes behaviour. Further work has to be performed in order to evaluate the inuence of other parameters, thus a reliable mathematical correlation between anode reducibility level and power density could be set up. The CuTbO2 SOFC performance is inuenced by the chemical hydrocarbon nature (C7H8 < n-C7H16 < C6H12 < C6 H@ ), it could be 12 explained considering the conductivity improvements produced by graphitic carbon deposits. In terms of maximum power density, SOFC efciency seems to be favoured by light hydrocarbons (low carbon/hydrogen ratio content). Moreover, the performance is improved by successive anode reactivations using hydrogen. Acknowledgement Authors would like to thank PDVSA-Intevep (Brazo Tecnolgico de Petrleos de Venezuela) for the permission of publishing this work.
Fig. 7. CuTbO2 SOFC Ej and Pj proles: (a) H2 ((h) 1H2, (s) 2H2, (4) 3H2 and 4H2) and (b) hydrocarbons ((h) n-C7H16, (s) C7H8, (4) C6H12 and C6 H@ ). 12

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C7H16 < C6H12 < This remark could be due to the conductivity improvement produced by graphitic carbon deposits, a similar behaviour have been reported for direct hydrocarbon copperceria SOFC [14]. SOFC performance seems to be favoured when the Cu TbO2 SOFC is operated with light hydrocarbons (low carbon/hydrogen ratio content). Moreover, the performance is improved by successive anode reactivations using hydrogen. 4. Conclusions Fundamentally, hydrocarbon conversion takes place at the anodic side of a SOFC; as a result, anode chemical nature is the initial aspects to be taken into consideration. Based on typical procedures and some minor modications, CuTbO2 and CuGd2O3 electrolyte supported SOFC were prepared by using the following methods: tape casting, dual tape casting, painting and impregnation. The prepared YSZ (electrolyte) was compact and dense, its thickness

C6 H@ . 12

[13] [14] [15] [16] [17]