Electro-catalytic conformal coatings and method for making the same
09914649 ยท 2018-03-13
Assignee
Inventors
Cpc classification
H01M4/9033
ELECTRICITY
C01P2002/76
CHEMISTRY; METALLURGY
H01M4/905
ELECTRICITY
C01G51/006
CHEMISTRY; METALLURGY
C01G51/56
CHEMISTRY; METALLURGY
C01P2002/77
CHEMISTRY; METALLURGY
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
H01M4/8621
ELECTRICITY
C01P2002/72
CHEMISTRY; METALLURGY
International classification
H01M4/86
ELECTRICITY
Abstract
A composition of matter is disclosed which is a perovskite having a composition A.sub.2xA.sub.xB.sub.2yB.sub.yO.sub.6, where A is a praseodymium (Pr) element at the A-site of the perovskite, A is a strontium (Sr) element at the A-site of the perovskite, B is a cobalt (Co) element at the B-site of the perovskite, and B is a manganese (Mn) element at the B-site of the perovskite, and where 0<x 1 and 0<y<2. Also disclosed is an electrode material Conformally coated with the composition of matter. Also disclosed are methods of producing the composition of matter and conformally coating the electrode material. Also disclosed an electrode is conformally coated with a praseodymium strontium manganese perovskite and a method for the coating.
Claims
1. An electrode of comprising: a porous mixed ionic-electronic conductor (MIEC); and an oxygen-reducing catalyst coating having a thickness in a range from about 1 to about 50 nm; wherein the oxygen-reducing catalyst coating comprises a perovskite having a composition A.sub.1xA.sub.xBO.sub.3; wherein A comprises a praseodymium (Pr) element at the A-site of the perovskite, A comprises a strontium (Sr) element at the A-site of the perovskite, and B comprises a manganese (Mn) element at the B-site of the perovskite; and wherein 0x<1.
2. An electrode comprising: a porous mixed ionic-electronic conductor (MIEC); and an oxygen-reducing catalyst coating having a thickness in a range from about 1 to about 50 nm; wherein the oxygen-reducing catalyst coating comprises a perovskite having a composition A.sub.2xA.sub.xB.sub.2yB.sub.yO.sub.6; wherein A comprises a praseodymium (Pr) element at the A-site of the perovskite, A comprises a strontium (Sr) element at the A-site of the perovskite, B comprises a cobalt (Co) element at the B-site of the perovskite, and B comprises a manganese (Mn) element at the B-site of the perovskite; and wherein 0<x1.2 and 0<y<2.
3. The electrode of claim 2, wherein x>0 and y>0, such that the oxygen-reducing catalyst coating is praseodymium strontium cobalt manganese (PSCM).
4. The electrode of claim 2, wherein 0.2<x1.2 and 0.2<y<1.9.
5. The electrode of claim 2, wherein 0.4<x1.1 and 0.8<y<1.2.
6. The electrode of claim 2, wherein x=1 and y=1.
7. A solid-oxide fuel cell comprising: an electrolyte; an anode electrically coupled to a first surface of the electrolyte; and a cathode electrically coupled to a second surface of the electrolyte, the cathode comprising the electrode of claim 1.
8. The electrode of claim 1, wherein the porous mixed ionic-electronic conductor is selected from a group consisting of lanthanum strontium manganite (LSM), lanthanum strontium cobalt ferrite (LSCF), strontium-doped samarium cobaltite (SSC), barium strontium cobalt ferrite (BSCF), praseodymium barium cobalt (PBC) and their derivatives.
9. The electrode of claim 1, wherein the oxygen-reducing catalyst coating is a continuous film.
10. The electrode of claim 1, wherein the electrode has a first interfacial resistance less than or equal to about 0.1 cm.sup.2 at about 750 C.
11. The electrode of claim 1, wherein x>0, such that the oxygen-reducing catalyst coating is praseodymium strontium manganese (PSM).
12. The electrode of 1, wherein x<0.5.
13. The electrode of claim 1, wherein 0.1<x<0.3.
14. The electrode of claim 1, wherein x=0.25.
15. The electrode of claim 2, wherein the porous mixed ionic-electronic conductor is selected from a group consisting of lanthanum strontium manganite (LSM), lanthanum strontium cobalt ferrite (LSCF), strontium-doped samarium cobaltite (SSC), barium strontium cobalt ferrite (BSCF), praseodymium barium cobalt (PBC) and their derivatives.
16. The electrode of claim 2, wherein the oxygen-reducing catalyst coating is a continuous film.
17. The electrode of claim 2, wherein the electrode has a first interfacial resistance less than or equal to about 0.1 cm.sup.2 at about 750 C.
18. A solid-oxide fuel cell comprising: an electrolyte; an anode electrically coupled to a first surface of the electrolyte; and a cathode electrically coupled to a second surface of the electrolyte, the cathode comprising the electrode of claim 2.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION
(14) To facilitate an understanding of the principals and features of the disclosed technology, illustrative embodiments are explained below. The compounds and components described hereinafter as making up various elements of the disclosed technology are intended to be illustrative and not restrictive. Many suitable compounds or components that would perform the same or similar functions as components described herein are intended to be embraced within the scope of the disclosed electronic devices and methods. Such other components not described herein may include, but are not limited to, for example, components developed after development of the disclosed technology.
(15) It must also be noted that, as used in the specification and the appended claims, the singular forms a, an and the include plural referents unless the context clearly dictates otherwise.
(16) By comprising or containing or including is meant that at least the named compound, element, particle, or method step is present in the composition or article or method, but does not exclude the presence of other compounds, materials, particles, method steps, even if the other such compounds, material, particles, method steps have the same function as what is named.
(17) By blank or un-infiltrated or uncoated is meant that a surface coating has not been applied to the substance or component in question. By infiltrated or coated or conformally coated is meant that a surface coating has been applied to the substance or component in question.
(18) It is also to be understood that the mention of one or more method steps does not preclude the presence of additional method steps or intervening method steps between those steps expressly identified. Similarly, it is also to be understood that the mention of one or more components in a device or system does not preclude the presence of additional components or intervening components between those components expressly identified.
(19) Referring now to the Figures, in which like reference numerals represent like parts, various embodiments of the compounds, cathodes, coatings, and methods will be disclosed in detail.
(20) This disclosure describes two perovskite compounds and certain applications of those compounds: Pr.sub.0.75Sr.sub.0.2MnO.sub.3 (PSM) and a new perovskite compound, PrSrCoMnO.sub.6 (PSCM). As explained in this disclosure, these compounds may be useful as conformal catalytic coatings for porous electrochemical cathodes, among other uses. PSM and PSCM are both derivatives of the doped lanthanide manganite structure, an extensively explored group of materials exhibiting good performance as SOFC cathode materials. In certain embodiments, the perovskite structure of PSM and PSCM allows them to form a conformal coating on LSCF, which is also a perovskite, as well as other perovskite materials. A desire for superior oxygen exchange activity motivated the choice of Pr in the A site 104. Similar performance is sometimes noted by this element in both the Ln.sub.1xSr.sub.xMnO.sub.3 series and LnSrCoMnO.sub.6 series of materials (where Ln represents the lanthanide elements from Ln to Gd). A desire to increase the catalytic activity without giving up all of the benefit of stability motivated the choice to substitute cobalt in the B site of lanthanide manganite. Some perovskite cathodes with Mn in the B-site are known for their stability over long term operation while some cobaltites show higher ionic and electronic conductivities.
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(23) TABLE-US-00001 TABLE 1 Estimated structural parameters of PSCM by Rietveld method Space group Pnma(No. 62).sup.A a({acute over ()}) 5.3802(8) b({acute over ()}) 7.6318(4) c({acute over ()}) 5.4204(3) V({acute over ()}.sup.3) 222.57(1) Z 4 (nominal) 0.07 <Mn/CoO> ({acute over ()}) 1.932(1).sup.b .sup.AAtomic crystal sites are adopted from as: Pr/Sr, 4c(x, , z); Mn/Sr, 4b(x, y, ); O(1), 4c(x, , z); O(2), 8d(x, y, z); x, y, z are refinement parameters. .sup.bMn/CoO(1), 1.923(1) {acute over ()} 2; Mn/CoO(2), 1.902(1) {acute over ()} 2; Mn/CoO(2), 1.970(1) {acute over ()} 2
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(27) Method of Preparing LSM, PSM and PSCM Infiltration Solutions and Catalytic Coating:
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(29) In order to identify the phase of the proposed catalysts, PSM and PSCM powders were synthesized using the same solution process as for coating. After self-combustion, the ashes were collected and fired at 900 C. for 1 hour. The structural analysis for the PSM and PSCM powders are discussed above.
(30) Method of Fabricating Symmetrical Cells as Well as Three-Electrode Configurations:
(31) YSZ pellets were prepared by uniaxially pressing a commercially available YSZ powder into a green pellet. The green pellets were then sintered at 1450 C. for 5 hours to achieve a relative density of 98%. LSCF. Green tapes prepared by tape-casting were then bound onto both sides of a YSZ pellet using a slurry of Sm.sub.0.2Ce.sub.0.8O.sub.2 as a buffer layer, which was subsequently co-fired with SDC on YSZ at 1080 C. for 2 hours to form porous LSCF electrodes with an active area of 0.3 cm.sup.2.
(32) The SDC powder was synthesized using a chemical co-precipitation process. The SDC powder was then dispersed in acetone with V-006 (Heraeus, US) as binder and ball-milled for 24 hours to form a stable SDC slurry. The symmetrical cells were also employed for a three-electrode configuration. The LSCF cathode with/without catalyst coating were used as working electrode (WE) and counter electrode (CE), respectively. Platinum (Pt) paste was fired at 900 C. for 1 hour as reference electrode (RE) by positioning it as close to working electrode as possible.
(33) Methods of Fabricating Anode-Supported Full Cells:
(34) Tape-cast NiO/YSZ anode-support was first fabricated and pre-fired at 850 C. for 2 h. Then, an active NiO/YSZ layer (15 m) and a YSZ electrolyte (15 m) were sequentially deposited on the anode support by a particle suspension coating process followed by co-firing at 1400 C. for 5 h.[32] The LSCF cathode was then applied to the YSZ electrolyte using the same procedures for the fabrication of symmetric cells as described earlier.
(35) The phase compositions of LSCF, PSM and PSCM powders as well as their composites were determined by XRD. LSCF powders were fired at 1080 C. for 2 hours (as the same as the fabrication process of cathode backbone). PSM and PSCM powder precursors were first obtained from a glycine-combustion method and then fired at 900 C. for 1 hour (the same as the fabrication process for their coating). Their composites were obtained by putting LSCF powders (1080 C./2 hours) into PSM and PSCM individual solution (ultimate powder weight ratio=50:50) to dry in oven and fired at 900 C. for one hour. Raman spectroscopy was performed using 514 nm laser excitation on mixed PSM-LSCF and PSCM-LSCF samples that were annealed at 1000 C. for 100 hours for further chemical analysis. The microstructure and morphology of the LSCF pellets with/without catalysts coatings were examined using a scanning electron microscope.
(36) Coating Thickness
(37) The thickness of the catalytic coating may be estimated from the following equation:
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(39) V is solution volume, C is solution concentration, M is the molar weight of the infiltration material, is the theoretical density of the infiltration material, and S is the inner surface area of porous cathode that was coated with the solution. In the experimental embodiment, V, C, and S were held constant, so that L was determined mainly by the ratios of M/, which did not vary much among LSM, PSM and PSCM (from the range was 35 to 37 mol cm.sup.3 g.sup.2). Therefore, the thicknesses of PSM and PSCM coatings are most likely comparable to that of the LSM coating, which is based on a prior TEM observation (in M. E. Lynch, L. Yang, W. Qin, J.- J. Choi, M. Liu, K. Blinn, and M. Liu, Energy & Environmental Science, 2011, 4, 2249, incorporated by reference in its entirety) varying in the 2-23 nm range.
(40) Electrochemical Measurements:
(41) The area-specific resistance (ASR) of the cathodes was measured in a two-electrode symmetric-cell configuration using two pieces of Pt mesh as current collector (without Pt paste to avoid the possible catalytic contribution from Pt) at 500-800 C. Impedance was measured across a broad frequency spectrum using a frequency response analyzer interfaced with an potentiostat. The amplitude was set to 10 mV, from 100 kHz to 0.1 Hz. The overpotential, , was calculated using the following equation:
=U.sub.WRiR.sub.ohm(2)
(42) U.sub.WR is the constant potential applied between WE and RE, i is the corresponding current density, and R.sub.ohm is the ohmic resistance of the cell. The current response of the cell reached a steady state after the DC polarization was applied for 30 min. To accurately determine the ohmic resistance of the cell, impedance spectra were also collected under identical DC polarization after the cell response was stabilized. The button cells were mounted on an alumina supporting tube for fuel cell testing at 750 C. with humidified hydrogen (3% H2O) as the fuel and stationary air as the oxidant. The cell performance was monitored with an Arbin multi-channel electrochemical testing system.
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(50) The composition, design, and functionality described in this application is intended to be exemplary in nature and is not intended to limit the instant disclosure in any way. Those having ordinary skill in the art will appreciate that the teachings of the disclosure may be implemented in a variety of suitable forms, including those forms disclosed herein and additional forms known to those having ordinary skill in the art.
(51) While certain embodiments of this disclosure have been described in connection with what is presently considered to be the most practical and various embodiments, it is to be understood that this disclosure is not to be limited to the disclosed embodiments, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the scope of the appended claims. Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
(52) This written description uses examples to disclose certain embodiments of the technology and also to enable any person skilled in the art to practice certain embodiments of this technology, including making and using any apparatuses or systems and performing any incorporated methods. The patentable scope of certain embodiments of the technology is defined in the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.