Electrolyte formation for a solid oxide fuel cell device

Abstract

A method of fabricating a SSZ/SDC bi-layer electrolyte solid oxide fuel cell, comprising the steps of: fabricating an NiO-YSZ anode substrate from a mixed NiO and yttria-stabilized zirconia by tape casting; sequentially depositing a NiO-SSZ buffer layer, a thin SSZ electrolyte layer and a SDC electrolyte on the NiO-YSZ anode substrate by a particle suspension coating or spraying process, wherein the layers are co-fired at high temperature to densify the electrolyte layers to at least about 96% of their theoretical densities; and painting/spraying a SSC-SDC slurry on the SDC electrolyte to form a porous SSC-SDC cathode. A SSZ/SDC bi-layer electrolyte cell device and a method of using such device are also discussed.

Claims

1. A method of using a SSZ/SDC bi-layer electrolyte cell, comprising: providing a SSZ/SDC bi-layer electrolyte cell, the SSZ/SDC bi-layer electrolyte cell fabricated by: fabricating a NiO-YSZ anode substrate from a mixed NiO and yttria-stabilized zirconia by tape casting; sequentially depositing a NiO-SSZ buffer layer, a thin SSZ electrolyte layer, and a SDC electrolyte on the NiO-YSZ substrate by a particle suspension coating process to form an active layer, wherein the NiO-SSZ buffer layer is about 25 m thick, the SSZ electrolyte layer is about 1m thick, the SDC electrolyte is about 5 m thick; co-firing the active layer at a temperature in a range of between 1200 C. and 1375 C. to densify the electrolyte layers to at least about 96% of their theoretical densities prior to application of a cathode; and painting a SSC-SDC slurry on the co-fired SDC electrolyte layer to form a porous SSC-SDC cathode; operating the SSZ/SDC bi-layer electrolyte cell to convert fuel to electricity, operating comprising: providing a fuel at the anode and an oxidant at the cathode, the fuel selected from the group consisting of hydrogen, hydrocarbons, coal gas, bio-derived fuels, other renewable solid wastes and mixtures thereof, and the oxidant selected from the group consisting of air, oxygen and mixtures thereof; maintaining the SSZ/SDC bi-layer electrolyte cell at an intermediate temperature of between 600 to 700 C. while operating; and achieving a fuel-to-electricity efficiency of at least 60% while operating at the intermediate temperature.

2. The method of claim 1, wherein the NiO and yttria-stabilized zirconia is mixed in a weight ratio of about 55:45.

3. The method of claim 1, wherein the NiO-YSZ anode substrate is fabricated to be about 200 to about 1000 m thick.

4. The method of claim 1, wherein the NiO-YSZ anode substrate is pre-fired at about 850 C. for about two hours.

5. The method of claim 1, wherein the SDC electrolyte is synthesized via a carbonate co-precipitation process or other wet-chemical process to form nano to submicron particles.

6. The method of claim 1, wherein the electrolyte layers are active layer is co-fired at high temperature to densify the electrolyte membranes.

7. The method of claim 1, wherein the active layer is co-fired at less than about 1300 C.

8. The method of claim 1, wherein the SSC-SDC slurry is formed by mixing SSC and SDC powders, binder and acetone.

9. The method of claim 1, wherein the SSC and SDC powders are mixed in a weight ratio of about 7:3.

10. The method of claim 1, wherein the SSC-SDC cathode is pre-fired at about 950 C. for about two hours.

11. The method of claim 1, wherein the NiO-YSZ anode substrate is fabricated to be about 800m thick.

12. The method of claim 1, wherein the SSZ/SDC bi-layer electrolyte cell is maintained at an intermediate temperature of between 600 to 650 C. while operating.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) For a further understanding of the nature and objects of the present inventions, reference should be made to the following detailed disclosure, taken in conjunction with the accompanying drawings, in which like parts are given like reference numerals, and wherein:

(2) FIG. 1A illustrates a chart of current density (A/cm.sup.2) verses voltage (V) and power density (W/cm.sup.2) for a SSZ/SDC bi-layer electrolyte cell tested with humidified hydrogen as fuel and ambient air as oxidant, co-fired at 1375 C., and operated at 600 C., 650 C. and 700 C.;

(3) FIG. 1B illustrates a chart of current density (A/cm.sup.2) verses voltage (V) and power density (W/cm.sup.2) for the SSZ/SDC bi-layer electrolyte cell tested with humidified hydrogen as fuel and ambient air as oxidant, co-fired at 1300 C., and operated at 600 C., 650 C. and 700 C.;

(4) FIG. 1C illustrates a chart of current density (A/cm.sup.2) verses voltage (V) and power density (W/cm.sup.2) for the SSZ/SDC bi-layer electrolyte cell tested with humidified hydrogen as fuel and ambient air as oxidant, co-fired at 1250 C., and operated at 600 C., 650 C. and 700 C.;

(5) FIG. 2 illustrates a chart of impedance response of SSZ/SDC bi-layer electrolyte cells co-fired at 1250 C., and operated at 600 C., 650 C. and 700 C. under OCV condition;

(6) FIG. 3 illustrates a chart of current density (A/cm.sup.2) verses voltage (V) and power density (W/cm.sup.2) for SSZ/SDC bi-layer electrolyte cells co-fired at 1250 C., 1300 C. and 1375 C., and operated at 650 C., showing the effect of co-firing temperature on the performance of the SSZ/SDC bi-layer;

(7) FIG. 4 illustrates impedance response of SSZ/SDC bi-layer electrolyte cells co-fired at 1250 C., 1300 C. and 1375 C., and operated at 650 C. under OCV condition, showing the effect of co-firing temperature on the impedance response on the SSZ/SDC bi-layer cells;

(8) FIG. 5A illustrates a cross-sectional view of the SSZ/SDC bi-layer electrolyte cell co-fired at 1250 C.;

(9) FIG. 5B illustrates an expanded cross-sectional view of the SSZ/SDC electrolyte layer for the SSZ/SDC bi-layer electrolyte cell of FIG. 5A; and

(10) FIG. 6 illustrates a chart of time (hours) verses power density (W/cm.sup.2) for the SSZ/SDC bi-layer electrolyte cell tested with humidified hydrogen and ambient air, co-fired at 1250 C., and operated at 650 C. under constant voltage of about 0.7 V, showing the stability of the SSZ/SDC bi-layer electrolyte cell under hydrogen fuel.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION

(11) The following detailed description of various embodiments of the present invention references the accompanying drawings, which illustrate specific embodiments in which the invention can be practiced. While the illustrative embodiments of the invention have been described with particularity, it will be understood that various other modifications will be apparent to and can be readily made by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the examples and descriptions set forth herein but rather that the claims be construed as encompassing all the features of patentable novelty which reside in the present invention, including all features which would be treated as equivalents thereof by those skilled in the art to which the invention pertains. Therefore, the scope of the present invention is defined only by the appended claims, along with the full scope of equivalents to which such claims are entitled.

(12) This invention discloses the formation and application of the SSZ/SDC bi-layer electrolyte for intermediate temperature SOFC applications. See FIGS. 1 and 5. As illustrated in FIG. 5A, a conventional NiO-YSZ substrate was used to support the thin membrane cell. In an embodiment, the SSZ electrolyte film is thin enough (about 1 m) to reduce the ohimic resistance but thick enough to block the electronic conduction of the SDC electrolyte membrane. See FIGS. 5A & 5B. In an embodiment, a high reactive SDC powder, synthesized via a carbonate co-precipitation method [20], was used for SDC membrane fabrication to lower the sintering temperature of electrolyte membranes. In an embodiment, the new SOFC configuration provided excellent performance at the operating temperatures of 600 C. to 700 C.

EXAMPLES

(13) SOFC Fabrication: Button cells with a configuration Ni-YSZ/Ni-SSZ/SSZ/SDC/SSC-SDC were fabricated. First, a NiO-YSZ anode substrate was fabricated from a mixed NiO (Alfa) and yttria-stabilized zirconia (8YSZ, Daiichi Kigenso, Japan) (weight ratio of about 55:45) by tape casting (about 800 m thick and punched to about inch in diameter), followed by pre-firing at about 850 C. for about 2 hours. See e.g., FIG. 5A. In an embodiment, the NiO-YSZ anode substrate may be fabricated to be about 200 to about 1000 m thick. Second, a NiO-SSZ buffer ((Sc.sub.2O.sub.3).sub.0.1(CeO.sub.2).sub.0.01(ZrO.sub.2).sub.0.89), Fuel Cell Materials) (about 25 m), a thin SSZ electrolyte layer (about 1 m), and a SDC electrolyte (Sm.sub.0.2Ce.sub.0.8O.sub.2-, synthesized via carbonate co-precipitation process [20, 21]) (about 15 m) were sequentially deposited on the NiO-YSZ anode substrate by a particle suspension coating process [22, 23] to form an active layer, followed by co-firing at high temperatures to densify the electrolyte layers. Id. In an embodiment, the thin SSZ electrolyte layer may be fabricated to be about 1 to about 5 m thick. In an embodiment, the SDC electrolyte may be fabricated to be about 10 to about 50 m thick. In an embodiment, the active layer was co-fired at about 1200 C. to about 1400 C. to densify the electrolyte layers to about 96% to about 98% of their theoretical densities. In other words, the original thickness of the electrolyte layers is reduced by about 20%. Id. In an embodiment, the active layer was co-fired at about 1250 C. to densify the electrolyte layers to about 96% of their theoretical densities. Finally, SSC and SDC powders at a weight ratio of about 7:3 were mixed with a binder (V-006, Heraeus, Germany) and acetone to form a cathode slurry, which was brush-painted on the SDC electrolyte, followed by pre-firing at about 950 C. for about 2 hours to form a porous SSC-SDC cathode. Id.

(14) SOFC Testing: The whole SSZ/SDC bi-layer electrolyte cell was mounted and sealed on a fuel cell testing fixture, and then tested with humidified hydrogen or natural gas (Atlanta City Gas) as fuel and ambient air as oxidant. Suitable fuels include hydrogen, hydrocarbons (e.g., methane, natural gas, ethane, propane, butane, and C.sub.1 to C.sub.4 alcohols), coal gas, bio-derived fuels, and other renewable solid wastes and mixtures thereof, and suitable oxidants include ambient air, oxygen and mixtures thereof. The SSZ/SDC bi-layer electrolyte cell performance and the long-term electrochemical performance were examined with an Arbin multi-channel electrochemical testing system (MSTAT). AC impedance measurements were conducted using a Solartron 1255 HF frequency response analyzer, which was interfaced with an EG&G PAR potentiostat (Model 273A) with an amplitude of 10 mV in the frequency range from 100 kHz to 0.1 Hz.

(15) Effect of Sintering Temperature: In a bi-layer electrolyte structure, the inter-diffusion (or reaction) between electrolyte layers at co-firing conditions is a primary concern [16, 18, 19]. It has been previously reported that the inter-diffusion formed the (Zr,Ce)O.sub.2-based solid solution, the conductivity of which is 2-4 times lower than that of the SSZ, is one to two orders of magnitude lower than that of the SDC [19]. Table 1 includes the ionic conductivity (.sub.i) and electronic conductivity (.sub.e) of YSZ, GDC, and the mixed composites at 800 C. [19].

(16) TABLE-US-00001 TABLE 1 Ionic conductivity (.sub.i) and electronic conductivity (.sub.e) of YSZ, GDC and the mixed composites at 800 C. [19] Material Nominal composition .sub.i (Sm.sup.1) .sub.e (Sm.sup.1) YSZ Zr.sub.0.85Y.sub.0.15O.sub.1.93 5.4 .sup.7.29 10.sup.11 GDC Ce.sub.0.80Gd.sub.0.20O.sub.1.56 8.7 8.18 10.sup.4 Reaction Ce.sub.0.37Zr.sub.0.38Gd.sub.0.18Y.sub.0.07O.sub.1.67 0.125 3.99 10.sup.4 product Interlayer Ce.sub.0.43Zr.sub.0.43Gd.sub.0.10Y.sub.0.04O.sub.1.93 0.603 3.88 10.sup.4

(17) FIGS. 1A-1C illustrate performance data for three SSZ/SDC bi-layer electrolyte cells tested with humidified hydrogen at the anode and ambient air at the cathode, co-fired at 1375 C., 1300 C. and 1250 C., respectively, and operated at 600 C., 650 C. and 700 C. As expected, the performance of the SSZ/SDC bi-layer electrolyte cells increases as co-firing temperature decreases. For example, the maximum power densities are about 0.67 W/cm.sup.2, about 0.75 W/cm.sup.2 and about 1.05 W/cm.sup.2 for the SSZ/SDC bi-layer electrolyte cells co-fired at 1375 C., 1300 C. and 1250 C., respectively, and operated at 700 C. See FIGS. 1A-1C. The higher performance achieved at lower firing temperature may be due to the fact that lower co-firing temperatures alleviate the reaction/inter-diffusion between SSZ and SDC. Id. At corresponding test temperatures, the OCV of the SSZ/SDC bi-layer electrolyte cells decreases as co-firing temperatures increase. See e.g., FIGS. 2 & 4. In these SSZ/SDC bi-layer electrolyte cells, the thickness of the SSZ and SDC layers are about 1 m and about 15 m, respectively. See FIGS. 5A-5B. The lower OCV achieved in the SSZ/SDC bi-layer electrolyte cell when co-fired at higher temperature may be due to the inter-diffusion between SSZ and SDC, which consumes the SSZ layer and reduces the contribution of electronic blocking effect from SSZ. See FIGS. 2 & 4. At a co-firing temperature of 1250 C., however, the SZZ/SDC bi-layer electrolyte cell reached a high OCV and an excellent performance. See FIG. 2. The OCV values are about 1.022 V, about 1.041 V, and about 1.057 V at operating temperatures of 700 C., 650 C., and 600 C., respectively. Id. These OCV values are very close to the theoretical Nernst potentials, indicating that the about 1 m thick SSZ electrolyte layer co-fired with SDC significantly blocks the electronic conduction of SDC at these operating conditions. Maximum powder densities of the cell are about 1.05 W/cm.sup.2, about 0.66 W/cm.sup.2, and about 0.32 W/cm.sup.2 at operating temperatures of 700 C., 650 C., and 600 C., respectively. See FIG. 1C. The performance is much higher than previous results with the YSZ/SDC, BCS/SDC SSZ/SDC bi-layer structures, indicating that the reducing the co-firing temperature of SSZ/SDC bi-layer will be an important approach to best utilize the SDC electrolyte for intermediate temperature SOFCs with enhanced energy conversion efficiency.

(18) FIG. 3 illustrates a comparison of three SSZ/SDC bi-layer electrolyte cells co-fired at 1250 C., 1300 C. and 1375 C., respectively, and operated at 650 C. Clearly, both the performance and the OCV are increased as co-firing temperatures are decreased. Id. As discussed above, the higher co-firing temperatures increase the inter-diffusion of the SSZ and SDC, which was further confirmed by the impedance results shown in FIG. 4. Both bulk resistance and interfacial resistance are increased as the co-firing temperature is increased. See FIGS. 3 & 4.

(19) A SSZ/SDC bi-layer electrolyte cell structure is illustrated in FIG. 5. FIG. 5A shows a cross-sectional view of the SSZ/SDC bi-layer electrolyte cell co-fired at 1250 C., and FIG. 5B shows an expanded cross-sectional view of the SSZ/SDC bi-layer electrolyte layer of the SSZ/SDC bi-layer electrolyte cell co-fired at 1250 C. The SSC-SDC layer forms the cathode, SDC and SSZ layers form the electrolyte, and the Ni-SSZ and Ni-YSZ layers form the anode. See FIG. 5A. As illustrated in FIG. 5A, a uniform thin layer of Ni-SSZ, SSZ and SDC is deposited (and well-adhered) to the porous Ni-YSZ anode substrate. As discussed above, the thickness of the Ni-SSZ, SSZ and SDC layers is about 25 m, about 1 m, and about 15 m, respectively. See FIG. 5A.

(20) FIG. 6 illustrates a stability test of the SSZ/SDC bi-layer electrolyte cell with humidified hydrogen and ambient air, co-fired at 1250 C., and operated at 650 C. under a constant voltage of about 0.7 V. A stable power density output of about 0.51 W/cm.sup.2 at an operating temperature of 650 C. was demonstrated during the 50+ hour test period, showing good potential for practical application in a SOFC. With humidified hydrogen as fuel and ambient air as oxidant, the SSZ/SDC bi-layer electrolyte cell achieved a fuel to electrical efficiency of about 64% at 0.8 V and an operating temperature of 650 C.

(21) In subsequent testing, a stability test SSZ/SDC bi-layer electrolyte cell with humidified hydrogen, carbon dioxide and ambient air, co-fired at 1250 C., and measured at 650 C. under constant voltage of about 0.7 V indicated that the SOFC configuration was stable. The humidified hydrogen and carbon dioxide gases were mixed in a volume ratio of about 80:20. A stable power density output of about 0.42 W/cm.sup.2 at an operating temperature of 650 C. was demonstrated during the testing, showing good potential for practical application with natural gas as fuel. With humidified hydrogen and carbon dioxide mixture as fuel and ambient air as oxidant, the SSZ/SDC bi-layer electrolyte cell achieved a fuel to electrical efficiency of about 64% at 0.8 V and an operating temperature of 650 C.

(22) It should be noted that the performance of the new SOFC configuration can be further enhanced through surface modification process as developed in our other inventions [24].

(23) The embodiments and examples set forth herein are presented to best explain the present invention and its practical application and to thereby enable those skilled in the art to make and utilize the invention. However, those skilled in the art will recognize that the foregoing description and examples have been presented for the purpose of illustration and example only. The description as set forth is not intended to be exhaustive or to limit the invention to the precise form disclosed. Many modifications and variations are possible in light of the above teaching without departing from the spirit and scope of the following claims.

DEFINITIONS

(24) As used herein, the terms a, an, the, and said means one or more.

(25) As used herein, the term about means the stated value plus or minus a margin of error or plus or minus 10% if no method of measurement is indicated.

(26) As used herein, the term and/or, when used in a list of two or more items, means that any one of the listed items can be employed by itself, or any combination of two or more of the listed items can be employed. For example, if a composition is described as containing components A, B, and/or C, the composition can contain A alone; B alone; C alone; A and B in combination; A and C in combination; B and C in combination; or A, B, and C in combination.

(27) As used herein, the terms comprising, comprises, and comprise are open-ended transition terms used to transition from a subject recited before the term to one or more elements recited after the term, where the element or elements listed after the transition term are not necessarily the only elements that make up the subject.

(28) As used herein, the terms containing, contains, and contain have the same open-ended meaning as comprising, comprises, and comprise, provided above.

(29) As used herein, the terms having, has, and have have the same open-ended meaning as comprising, comprises, and comprise, provided above.

(30) As used herein, the terms including, includes, and include have the same open-ended meaning as comprising, comprises, and comprise, provided above.

(31) As used herein, the phrase consisting of is a closed transition term used to transition from a subject recited before the term to one or more material elements recited after the term, where the material element or elements listed after the transition term are the only material elements that make up the subject.

(32) As used herein, the phrase consisting essentially of occupies a middle ground, allowing the addition of non-material elements that do not substantially change the nature of the invention, such as various buffers, differing salts, extra wash or precipitation steps, pH modifiers, and the like.

(33) As used herein, the term simultaneously means occurring at the same time or about the same time, including concurrently.

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INCORPORATION BY REFERENCE

(58) All patents and patent applications, articles, reports, and other documents cited herein are fully incorporated by reference to the extent they are not inconsistent with this invention.