Reinforced matrix for molten carbonate fuel cell and method for manufacturing the same
11205795 · 2021-12-21
Assignee
Inventors
- Arun SURENDRANATH (Danbury, CT, US)
- Abdelkader Hilmi (Bethel, CT, US)
- Chao-Yi Yuh (New Milford, CT, US)
Cpc classification
H01M4/9033
ELECTRICITY
Y02P70/50
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
Y02E60/50
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
H01M4/905
ELECTRICITY
H01M8/142
ELECTRICITY
International classification
H01M4/86
ELECTRICITY
Abstract
A reinforced electrolyte matrix for a molten carbonate fuel cell includes a porous ceramic matrix, a molten carbonate salt provided in the porous ceramic matrix, and at least one reinforcing structure comprised of at least one of yttrium, zirconium, cerium or oxides thereof. The reinforcing structure does not react with the molten carbonate salt. The reinforced electrolyte matrix separates a porous anode and a porous cathode in the molten carbonate fuel cell.
Claims
1. A reinforced electrolyte matrix for a molten carbonate fuel cell comprising: a porous ceramic matrix; a molten carbonate salt provided in the porous ceramic matrix; and at least one reinforcing structure comprising: (a) rod, fiber, whisker, or boulder consisting of yttrium, cerium, zirconium, yttria, ceria, zirconia, or alumina, and coated with a protective film of yttria-stabilized zirconia, yttria, zirconia, yttria-aluminate, or ceria on the surface of the rod, fiber, whisker or boulder; (b) an alumina-zirconia boulder comprising a eutectic ceramic material including alumina and zirconia; or (c) combinations thereof; wherein the reinforcing structure does not react with the molten carbonate salt.
2. The reinforced electrolyte matrix of claim 1, wherein the reinforcing structure comprises (a) the rod, fiber, whisker, or boulder consisting of yttrium, cerium, zirconium, yttria, ceria, zirconia, or alumina, and coated with a protective film of yttria-stabilized zirconia, yttria, zirconia, yttria-aluminate, or ceria on the surface of the rod, fiber, whisker, or boulder.
3. The reinforced electrolyte matrix of claim 1, wherein the reinforcing structure comprises (b) the alumina-zirconia boulder comprising a eutectic ceramic material including alumina and zirconia.
4. The reinforced electrolyte matrix of claim 3, wherein the alumina-zirconia boulder comprises alumina in an amount of 60 wt % and zirconia in an amount of 40 wt %.
5. The reinforced electrolyte matrix of claim 3, wherein an average particle size of the alumina-zirconia boulder is from 10 μm to 120 μm.
6. The reinforced electrolyte matrix of claim 1, wherein the reinforcing structure is a rod or a fiber consisting of yttrium, cerium, zirconium, yttria, ceria, zirconia, or alumina, and coated with a protective film of yttria-stabilized zirconia, yttria, zirconia, yttria-aluminate, or ceria on the surface of the rod or fiber and having an average diameter of 1 μm to 50 μm, and an average length of 10 μm to 100 μm.
7. The reinforced electrolyte matrix of claim 1, wherein the reinforcing structure is a yttria-coated alumina fiber, the alumina-zirconia boulder, or a combination thereof.
8. The reinforced electrolyte matrix of claim 1, wherein the reinforcing structure is present in an amount of 5 vol % to 30 vol % of a solid volume of the reinforced electrolyte matrix.
9. The reinforced electrolyte matrix of claim 1, further comprising at least one crack arrestor comprising alumina, lithium aluminate, or a combination thereof; wherein the crack arrestor is provided as a boulder, a fiber, or a rod.
10. The reinforced electrolyte matrix of claim 1, wherein: the porous ceramic matrix comprises lithium aluminate powder; and the molten carbonate salt comprises lithium carbonate, sodium carbonate, potassium carbonate, or combinations thereof.
11. The reinforced electrolyte matrix of claim 1, wherein the porous ceramic matrix comprises lithium aluminate powder, and is present in an amount of 10 vol % to 50 vol % of a solid volume of the reinforced electrolyte matrix.
12. The reinforced electrolyte matrix of claim 1, wherein the molten carbonate salt comprises at least one alkali carbonate.
13. The reinforced electrolyte matrix of claim 1, wherein the molten carbonate salt comprises lithium carbonate, potassium carbonate, sodium carbonate, or combinations thereof.
14. The reinforced electrolyte matrix of claim 1, wherein the rod or fiber consisting of yttrium, cerium, zirconium, yttria, ceria, zirconia, or alumina is coated with yttria or yttria-aluminate.
15. A molten carbonate fuel cell comprising: a porous anode; a porous cathode; and the reinforced electrolyte matrix of claim 1 provided between the porous anode and the porous cathode.
16. The molten carbonate fuel cell of claim 15, wherein: the porous anode comprises a porous nickel-based alloy anode; the porous cathode comprises a porous lithiated nickel oxide cathode; and in the reinforced electrolyte matrix, the porous ceramic matrix comprises lithium aluminate powder; and the molten carbonate salt comprises lithium carbonate, sodium carbonate, potassium carbonate, or combinations thereof.
17. A method of manufacturing a reinforced electrolyte matrix for a molten carbonate fuel cell, the method comprising: preparing a matrix slurry comprised of a solvent, lithium aluminate powder, carbonate salt, and at least one reinforcing structure comprising: (a) a rod, fiber, whisker, or boulder consisting of yttrium, cerium, zirconium, yttria, ceria, zirconia, or alumina, and coated with a protective film of yttria-stabilized zirconia, yttria, zirconia, yttria-aluminate, or ceria on the surface of the rod, fiber, whisker, or boulder; (b) an alumina-zirconia boulder comprising a eutectic ceramic material including alumina and zirconia; or (c) combinations thereof; tape casting the slurry; and drying the slurry to form the reinforced electrolyte matrix; wherein the reinforcing structure does not react with the carbonate salt.
18. The method of claim 17, wherein the reinforcing structure is present in an amount of 5 vol % to 30 vol % of a solid volume of the reinforced electrolyte matrix.
19. The method of claim 17, wherein the reinforcing structure comprises: a rod or a fiber consisting of yttrium, cerium, zirconium, yttria, ceria, zirconia, or alumina, and coated with yttria-stabilized zirconia, yttria, yttria-aluminate, zirconia, or ceria and having an average diameter of 1 μm to 50 μm and an average length of 10 μm to 100 μm; a boulder having an average particle size of 10 μm to 120 μm; or a combination thereof.
20. The method of claim 17, wherein prior to tape casting, the slurry further comprises at least one crack arrestor comprised of alumina, lithium aluminate, or a combination thereof, and wherein the crack arrestor is provided as a boulder, a fiber, or a rod.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The disclosure will become more fully understood from the following detailed description, taken in conjunction with the accompanying figures, in which:
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DETAILED DESCRIPTION
(10) Before turning to the figures, which illustrate the exemplary embodiments in detail, it should be understood that the present application is not limited to the details or methodology set forth in the description or illustrated in the figures. It should also be understood that the terminology is for the purpose of description only and should not be regarded as limiting.
(11) Referring to the figures, in general, embodiments of the present application are directed to a reinforced molten carbonate electrolyte matrix of a molten carbon fuel cell and a method of manufacturing the reinforced molten carbonate electrolyte matrix. A molten carbonate fuel cell assembly includes a porous anode (e.g., a porous nickel-based alloy anode such as a Ni—Al anode and/or a Ni—Cr anode) and a porous cathode (e.g., a porous lithiated nickel oxide cathode), separated by a molten carbonate electrolyte matrix. A molten carbonate electrolyte matrix includes molten carbonate salt stored in a porous ceramic matrix. The porous ceramic matrix may be, for example, a porous, unsintered lithium aluminate (LiAlO.sub.2) powder (α or γ-phase), while the molten carbonate salt may be, for example, lithium carbonate, potassium carbonate, sodium carbonate, or combinations thereof. In some examples, the molten carbonate salt may be any alkali carbonate that can be modified with alkali earth additives, for example, MgO, BaCO.sub.3, CaCO.sub.3 or SrCO.sub.3. The molten carbonate electrolyte matrix is impregnated with at least one reinforcing structure to form the reinforced molten carbonate electrolyte matrix described in the embodiments of the present application.
(12) The reinforcing structure does not react with the electrolyte and enhances the mechanical strength of the molten carbonate electrolyte matrix. The reinforcing structure is comprised of at least one of yttrium, zirconium, cerium or oxides thereof. In some examples, the reinforcing structure may be comprised of a substrate having a rod, fiber, whisker, or boulder shape and a coating for the substrate comprised of yttria-stabilized zirconia, yttria, zirconia or ceria. In other examples, the substrate itself is comprised of yttria-stabilized zirconia, yttria, zirconia or ceria formed in a rod, fiber, whisker, or boulder shape.
(13) In one example, the reinforcing structure may be one or more yttria-stabilized zirconia rods. See
(14) In another example, the reinforcing structure may be one or more yttria-coated alumina fibers. The yttria-coated alumina fibers may have an average diameter of 1 to 50 μm and an average length of 10 μm to 100 μm.
(15) In yet another example, the reinforcing structure may be one or more alumina-zirconia (Al.sub.2O.sub.3—ZrO.sub.2) boulders. In some aspects, the alumina-zirconia boulders may be a eutectic ceramic material comprised of 60 wt % Al.sub.2O.sub.3 and 40 wt % ZrO.sub.2. The average particle size of the alumina-zirconia boulders is 10 μm to 120 μm or 20 μm to 120 μm.
(16) In additional examples, the reinforcing structure may be any combination of yttria-stabilized zirconia rods, yttria-coated alumina fibers, and alumina-zirconia boulders. In some examples, a rod may have a slightly larger diameter than a fiber.
(17) The reinforcing structure may be present in an amount of 5 vol % to 30 vol % of the solid volume of the matrix. The reinforcing structures may be used alone to reinforce the matrix, or combined with traditional crack arrestors such as alumina boulder (large particles), alumina and/or lithium aluminate fibers/rods to reinforce the matrix. In some examples, the reinforcing support may be a mixture of baseline alumina and non-consuming electrolyte supports such as yttria-stabilized zirconia rods, yttria-coated alumina fibers, and alumina-zirconia boulders, where the amount of baseline alumina boulder may vary from 1 wt % to 50 wt % (i.e., wt % of the mixture of alumina and non-consuming electrolyte support. For example, if the mixture contains 10 wt % alumina, the balance will be 90 wt % of other stable supports.
(18) In some embodiments, the reinforced molten carbonate electrolyte matrix includes a mixture of lithium aluminate particulates, lithium precursor, metal additive, and at least one reinforcing structure. The lithium aluminate particulates form the porous matrix. The lithium aluminate particulates are present in an amount of 10 vol % to 50 vol % based on the solid volume. The lithium precursor may be lithium carbonate (i.e., the electrolyte). The metal additive may be comprised of traditional reinforcing metal aluminum particles or aluminum flakes. The at least one reinforcing structure includes at least one of yttria-stabilized zirconia rods, yttria-coated alumina fibers, alumina-zirconia boulders, and combinations thereof. The Al.sub.2O.sub.3—ZrO.sub.2 boulders may include 60 wt % Al.sub.2O.sub.3 and 40 wt % ZrO.sub.2.
(19) The reinforcing structures of the embodiments of the present application display higher stability in molten carbonate during conditioning and operation compared to the alumina rods and fibers disclosed in the prior art. Out-of-cell tests were conducted to evaluate the stability of yttria-stabilized zirconia rods, yttria-coated alumina fibers, and Al.sub.2O.sub.3—ZrO.sub.2 boulders in molten carbonate in air at temperature of 650° C. These tests were performed by mixing 10 g of reinforcing structures and 10 g of LiNa carbonate electrolyte, heating the mixture in air at a temperature of 650° C. for 150 hours, and then washing the samples with an acid solution composed of 70 vol % of glacial acetic acid and 30 vol % of anhydrous acetic to remove excess electrolyte and prepare samples for x-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), and surface morphology analyses. High resolution scanning electron microscope (SEM) analysis showed that after electrolyte immersion, alumina fibers exhibited a rough surface, indicating significant corrosion due to reaction with the molten electrolyte. See
Experiment 1—Method of Manufacturing Yttria-Coated Alumina Fibers
(20) In some embodiments, the reinforcing structure includes yttria-coated alumina fibers, for example, alumina fibers coated with yttria aluminate. One example of a method of manufacturing alumina fibers coated with yttria aluminate is illustrated in the flow chart of
(21) Electrolyte immersion tests were conducted in air at a temperature of 650° C. for 150 hours to assess the stability of the yttria aluminate coated alumina fibers. Post-test analysis showed good results in terms of phase stability and surface morphology of coated fibers. See SEM images of
Experiment 2—Method of Manufacturing Yttria-Stabilized Zirconia Rods and Comparison with Conventional Matrices
(22) In this example green tape matrices made with the reinforcing structures described above were prepared to evaluate strength, as well as the matrix gas sealing efficiency during operation and thermal cycling. A green tape matrix is made of at least two green layers that are laminated, each layer having the same composition. For example, a yttria-stabilized zirconia reinforced green tape matrix may be made of laminated green layers containing yttria-stabilized zirconia rods. Matrix slurries were prepared by mixing and milling (LiAlO.sub.2) support and carbonate electrolyte additives such as Li.sub.2CO.sub.3 in an organic solvent that is compatible with all the matrix ingredients (i.e., does not react with the matrix ingredients) such as methyl ethyl ketone (MEK) and/or a mixture of MEK and cyclohexane containing an appropriate dispersant such as fish oil (1-8 wt %) or Hypermer KD-1. The dispersant may be any dispersant that provides efficient de-agglomeration or deflocculation during the milling process. An attrition milling technique using YTZ® grinding media having 0.3 mm to 3 mm ball size with an average loading between 60 to 80 wt % and a grinding speed of approximately 2000 rpm is used to mill the mixture and achieve the desired average particle size, for example, less than 1 μm. After achieving the desired average particle size for the mixture containing LiAlO.sub.2 and carbonate electrolyte additive, other metal additives such as aluminum particles and/or aluminum flakes were added and milled to achieve a less than 1 μm average particle size.
(23) The slurry was separated into three portions. The first portion comprised Comparative Example 1, where a known amount of alumina boulder (10 vol % to 20 vol % of the dried green tape) was added to the slurry with an appropriate amount of a binder system (17 wt % to 22 wt %) containing acryloid B-72 and a plasticizer santicizer S160 (butyl benzyl phthalate) to prepare a baseline matrix.
(24) To form Comparative Example 2, a traditional crack arrestor, in particular, alumina fibers was added to the second portion of the slurry in an amount of 10 vol % to 20 vol % of the dried green tape, preferably, 15 vol %, with an appropriate amount of a binder system (17 wt % to 22 wt %) containing acryloid polymer B-72 and a plasticizer santicizer S160 (butyl benzyl phthalate). Only one type of crack arrestor was added to each slurry.
(25) To form Example 1, a reinforcing structure made of a plurality of yttria-stabilized zirconia rods was added to the third portion of the slurry in an amount of 10 vol % to 20 vol % of the dried green tape, for example, 15 vol %, with an appropriate amount of a binder system (17 wt % to 22 wt %) containing acryloid polymer B-72 and a plasticizer santicizer S160 (butyl benzyl phthalate).
(26) The slurries comprising Comparative Example 1, Comparative Example 2, and Example 1 were separately tape cast using a doctor blade and dried at about 50-60° C. for 20-60 minutes and laminated to form green tapes. The green tapes were then heat treated at approximately 500° C. for two hours and the products were used as the samples in a pore structure analysis and three-point bending tests (snap strength/bending measurements).
(27) Bending tests conducted on the samples showed that the reinforced matrix including yttria-stabilized zirconia rods (Example 1) exhibited significant improvement in strength compared to the baseline matrix (Comparative Example 1). Both the reinforced matrix including yttria-stabilized zirconia rods (Example 1) and the matrix including alumina fibers (Comparative Example 2) showed greater than 2 times improvement in snap strength vs. the conventional, baseline matrix (Comparative Example 1). See
Experiment 3—Use of Yttria-Stabilized Zirconia Rods in a Fuel Cell and Comparison with Conventional Matrix
(28) In order to highlight the benefit of yttria-stabilized zirconia reinforced matrix, several single fuel cells were built and operated under normal conditions (160 mA/cm.sup.2 and 75% fuel utilization) and subjected to thermal cycling tests from operating temperature (650° C.) to 150° C. to evaluate the matrix thermal cycle capability and gas sealing efficiency (crack resistance). Each single fuel cell assembly was comprised of a porous 80 wt % Ni—Al and 20 wt % Ni—Cr anode and a porous in-situ oxidized and lithiated NiO cathode, separated by a porous ceramic matrix (LiAlO.sub.2) (either a baseline matrix such as Comparative Example 1 in Experiment 2 or the reinforced matrix with yttria-stabilized zirconia rods such as Example 1 in Experiment 2). The cathode (250 cm.sup.2) was filled with an appropriate amount of Li/Na electrolyte and an appropriate amount of Li/Na electrolyte is also stored in cathode current collector to achieve the electrolyte balance required for life.
Experiment 4—Use of Alumina-Zirconia Boulders and Comparison with Conventional Matrix
(29) In order to evaluate the stability of a reinforcing structure comprised of alumina-zirconia boulders in molten carbonate electrolyte, several out-of-cell tests were conducted in air at 650° C. for 150 hours. The alumina-zirconia boulders evaluated were comprised of 60% alumina and 40% zirconia. High resolution SEM analysis of washed samples after electrolyte immersion tests showed no sign of corrosion or a very minor change on the surface of alumina-zirconia boulders (see
(30) The molten carbonate electrolyte matrices described above can also be manufactured using other techniques such as tape casting, pressure die casting, slip casting, extrusion, additive manufacturing techniques, or any other suitable method.
(31) The reinforced molten carbonate electrolyte matrices for molten carbon fuel cells described above can withstand higher mechanical and thermal stresses during cell operation, thermal cycling and transient conditions. Unlike conventional crack arrestors (e.g., alumina boulder (large particles), alumina and/or lithium aluminate fibers/rods) the reinforcing structures described above (e.g., yttria-stabilized zirconia rods, yttria-coated alumina fibers, alumina-zirconia boulders, and combination thereof) do not react with the molten carbonate electrolyte, thereby enhancing the mechanical strength of the molten carbonate electrolyte matrix.
(32) The construction and arrangements of the reinforced molten carbonate electrolyte matrix for molten carbon fuel cells and the methods of manufacturing the reinforced molten carbonate electrolyte matrix, as shown in the various exemplary embodiments, are illustrative only. Although only a few embodiments have been described in detail in this disclosure, many modifications are possible (e.g., variations in sizes, dimensions, structures, shapes and proportions of the various elements, values of parameters, mounting arrangements, use of materials, colors, orientations, image processing and segmentation algorithms, etc.) without materially departing from the novel teachings and advantages of the subject matter described herein. Some elements shown as integrally formed may be constructed of multiple parts or elements, the position of elements may be reversed or otherwise varied, and the nature or number of discrete elements or positions may be altered or varied. The order or sequence of any process, logical algorithm, or method steps may be varied or re-sequenced according to alternative embodiments. Other substitutions, modifications, changes and omissions may also be made in the design, operating conditions and arrangement of the various exemplary embodiments without departing from the scope of the present invention.
(33) As utilized herein, the terms “approximately,” “about,” “substantially”, and similar terms are intended to have a broad meaning in harmony with the common and accepted usage by those of ordinary skill in the art to which the subject matter of this disclosure pertains. It should be understood by those of skill in the art who review this disclosure that these terms are intended to allow a description of certain features described and claimed without restricting the scope of these features to the precise numerical ranges provided. Accordingly, these terms should be interpreted as indicating that insubstantial or inconsequential modifications or alterations of the subject matter described and claimed are considered to be within the scope of the invention as recited in the appended claims.
(34) References herein to the positions of elements (e.g., “top,” “bottom,” “above,” “below,” etc.) are merely used to describe the orientation of various elements in the FIGURES. It should be noted that the orientation of various elements may differ according to other exemplary embodiments, and that such variations are intended to be encompassed by the present disclosure.
(35) With respect to the use of substantially any plural and/or singular terms herein, those having skill in the art can translate from the plural to the singular and/or from the singular to the plural as is appropriate to the context and/or application. The various singular/plural permutations may be expressly set forth herein for the sake of clarity.