U.S. patent application number 15/417316 was filed with the patent office on 2017-06-29 for systems and methods for preventing chromium contamination of solid oxide fuel cells.
The applicant listed for this patent is VERSA POWER SYSTEMS LTD.. Invention is credited to Hongpeng HE, Anthony WOOD.
Application Number | 20170187048 15/417316 |
Document ID | / |
Family ID | 52808151 |
Filed Date | 2017-06-29 |
United States Patent
Application |
20170187048 |
Kind Code |
A1 |
HE; Hongpeng ; et
al. |
June 29, 2017 |
SYSTEMS AND METHODS FOR PREVENTING CHROMIUM CONTAMINATION OF SOLID
OXIDE FUEL CELLS
Abstract
In some embodiments, a solid oxide fuel system is provided. The
solid oxide fuel cell system may include a chromium-getter
material. The chromium-getter material may react with chromium to
remove chromium species from chromium vapor. The solid oxide fuel
cell system may also include an inert substrate. The
chromium-getter material may be coated onto the inert substrate.
The coated substrate may remove chromium species from chromium
vapor before the chromium species can react with a cathode in the
solid oxide fuel cell system.
Inventors: |
HE; Hongpeng; (Calgary,
CA) ; WOOD; Anthony; (Calgary, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
VERSA POWER SYSTEMS LTD. |
Danbury |
CT |
US |
|
|
Family ID: |
52808151 |
Appl. No.: |
15/417316 |
Filed: |
January 27, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
14220867 |
Mar 20, 2014 |
9559366 |
|
|
15417316 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01M 2008/1293 20130101;
B01D 53/02 20130101; B01J 20/3204 20130101; B01J 20/3236 20130101;
B01D 53/64 20130101; H01M 8/04089 20130101; Y02E 60/50 20130101;
H01M 8/0662 20130101; H01M 8/021 20130101; B01D 2251/408 20130101;
B01D 2251/304 20130101; B01D 2251/606 20130101; B01D 2253/1124
20130101; B01D 2251/602 20130101; H01M 4/9033 20130101; H01M 8/0228
20130101; H01M 4/8657 20130101; H01M 4/8892 20130101; B01D 2251/404
20130101; B01D 2251/302 20130101; B01D 2257/60 20130101 |
International
Class: |
H01M 8/0228 20060101
H01M008/0228; H01M 8/0662 20060101 H01M008/0662; B01J 20/32
20060101 B01J020/32; B01D 53/64 20060101 B01D053/64; B01D 53/02
20060101 B01D053/02; H01M 8/021 20060101 H01M008/021; H01M 4/90
20060101 H01M004/90 |
Claims
1. A method for reducing chromium contamination in a solid oxide
fuel cell system, the method comprising: coating a substrate with a
chromium-getter material such that the chromium-getter material is
bonded to the inert substrate, the chromium-getter material
comprising a material adapted to react with chromium to remove
chromium species from chromium vapor; and disposing the coated
substrate in the solid oxide fuel cell system, such that the coated
substrate removes chromium species from chromium vapor in the solid
oxide fuel cell system before the chromium species can react with a
cathode in the solid oxide fuel cell system.
2. The method of claim 1, wherein the chromium-getter material is
selected from the group consisting of lanthanum oxide, lanthanum
carbonate, and calcium carbonate.
3. The method of claim 1, wherein the chromium-getter material
comprises an inorganic carbonate, nitrate, hydroxide, or acetate
that reacts with chromium vapor in a range of 300 to 850.degree.
C.
4. The method of claim 3, wherein the chromium-getter material
further comprises at least one element selected from the group
consisting of lanthanum, barium, calcium, lithium, and sodium.
5. The method of claim 1, wherein the coated substrate is disposed
in a solid oxide fuel cell stack of the solid oxide fuel cell
system.
6. The method of claim 1, wherein the chromium-getter material
comprises a compound selected from the group consisting of barium
oxide, lithium oxide, and sodium oxide.
7. The method of claim 1, wherein the coated substrate is disposed
in a stack manifold and/or a stack hot box of the solid oxide fuel
cell system.
8. The method of claim 1, wherein the coated substrate is disposed
in a hot system piping of the solid oxide fuel cell system.
9. The method of claim 1, wherein the coated substrate is disposed
in an air flow stream of a solid oxide fuel cell interconnect of
the solid oxide fuel cell system.
10. The method of claim 1, wherein the coated substrate is disposed
in an area of the solid oxide fuel cell system that reaches a
temperature above about 300.degree. C. during use of the solid
oxide fuel cell system.
11. The method of claim 1, wherein the chromium-getter material
comprises pellets.
12. The method of claim 1, wherein the inert substrate is made of
alumina.
13. A method for reducing chromium contamination in a solid oxide
fuel cell, the method comprising: providing a chromium-getter
material, the chromium-getter material comprising a material
adapted to react with chromium to remove chromium species from
chromium vapor; and disposing the chromium-getter material inside
air flow channels of the solid oxide fuel cell, such that the
chromium-getter material removes chromium species from chromium
vapor in the solid oxide fuel cell before the chromium species can
react with a cathode in the solid oxide fuel cell.
14. The method of claim 13, wherein: the method further comprises
coating the chromium-getter material onto a substrate, and
disposing the chromium-getter material comprises disposing the
substrate inside the air flow channels of the solid oxide fuel
cell.
15. The method of claim 13, wherein the chromium-getter material is
selected from the group consisting of lanthanum oxide, lanthanum
carbonate, and calcium carbonate.
16. The method of claim 13, wherein the chromium-getter material
comprises an inorganic carbonate, nitrate, hydroxide, or acetate
that reacts with chromium vapor in a range of 300 to 850.degree.
C.
7. A solid oxide fuel cell system comprising: a chromium-getter
material comprising a material adapted to react with chromium to
remove chromium species from chromium vapor; and an inert
substrate, wherein the chromium-getter material is coated on and
bonded to the inert substrate, and the coated substrate is adapted
to remove chromium species from chromium vapor in the solid oxide
fuel cell system before the chromium species can react with a
cathode in the solid oxide fuel cell system.
18. The solid oxide fuel cell system of claim 17, wherein the
chromium-getter material is selected from the group consisting of
lanthanum oxide, lanthanum carbonate, and calcium carbonate.
19. The solid oxide fuel cell system of claim 17, wherein the
chromium-getter material comprises an inorganic carbonate, nitrate,
hydroxide, or acetate that reacts with chromium vapor in a range of
300 to 850.degree. C.
20. The solid oxide fuel cell system of claim 19, wherein the
chromium-getter material further comprises at least one element
selected from the group consisting of lanthanum, barium, calcium,
lithium, and sodium.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of U.S. patent application
Ser. No. 14/220,867 filed Mar. 20, 2014, and is related to U.S.
patent application Ser. No. 14/220,688 entitled "CATHODE CONTACT
LAYER DESIGN FOR PREVENTING CHROMIUM CONTAMINATION OF SOLID OXIDE
FUEL CELLS" by Anthony Wood et al., filed on Mar. 20, 2014, the
entire disclosures of which are incorporated herein by reference,
for all purposes, as if fully set forth herein.
BACKGROUND OF THE INVENTION
[0002] High temperature fuel cells such as solid oxide fuel cells
often include an electrolyte sandwiched between a cathode and an
anode. Oxygen combines with electrons at the cathode to form oxygen
ions which are conducted through an ion-conducting ceramic
electrolyte to the anode. At the anode, oxygen ions combine with
hydrogen and carbon monoxide to form water and carbon dioxide,
thereby liberating electrons and generating current.
[0003] Multiple fuel cells are stacked and interleaved with
interconnect plates, which distribute gases to the electrode
surfaces and act as current collectors. Volatile chromium species
from stainless steel components in the stack of cells, including
the interconnects, degrade performance of cathodes in the fuel
cells. These volatile species are carried in the airstream and
deposit at electrochemically active cathode regions causing
electrochemical cathode performance degradation. The degradation
may also be exacerbated in the presence of humidity, which is often
present in fuel cell stacks. The systems and methods described
herein provide solutions to these and other needs.
BRIEF SUMMARY OF THE INVENTION
[0004] In some embodiments, a solid oxide fuel system is provided.
The solid oxide fuel cell system may include a chromium-getter
material. The chromium-getter material may react with chromium to
remove chromium species from chromium vapor. The solid oxide fuel
cell system may also include an inert substrate. The
chromium-getter material may be coated onto the inert substrate.
The coated substrate may remove chromium species from chromium
vapor before the chromium species can react with a cathode in the
solid oxide fuel cell system.
[0005] A some embodiments, a method of reducing chromium
contamination in a solid oxide fuel cell stack may include coating
a substrate with a chromium-getter material to form a coated
substrate. The chromium getter material may react with chromium to
remove chromium species from chromium vapor. The method may include
disposing the coated substrate in the solid oxide fuel cell stack.
The coated substrate may remove chromium species from chromium
vapor in the solid oxide fuel cell before the chromium species can
react with a cathode in the solid oxide fuel cell stack.
[0006] In some embodiments, a method for reducing chromium
contamination in a solid oxide fuel cell may include providing a
chromium-getter material. The chromium-getter material may react
with chromium to remove chromium species from chromium vapor. The
method may include disposing the coated substrate inside air flow
channels of the solid oxide fuel cell. The chromium-getter material
may remove chromium species from chromium vapor in the solid oxide
fuel cell before the chromium species can react with a cathode in
the solid oxide fuel cell.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] The present invention is described in conjunction with the
appended figures:
[0008] FIG. 1 shows an example portion of one possible fuel cell
stack embodiment of the invention in an exploded view;
[0009] FIG. 2 shows an example cross section of one possible fuel
cell stack of the invention;
[0010] FIG. 3 is a scanning electron microscope (SEM) photograph of
a multilayer contact material in between a fuel cell and an
interconnect in one embodiment of the invention;
[0011] FIG. 4 shows an example process flow diagram of one possible
fuel cell system of the invention;
[0012] FIG. 5 is a block diagram of one embodiment of the invention
for reducing chromium contamination;
[0013] FIG. 6 shows of the results of a cathode performance test
using a barium carbonate powder blended with a contact paste and
applied to a single cell;
[0014] FIG. 7 is a graph of fuel cell voltage against time at fixed
current density and gas flows for each of a reference case, a
calcium-containing additive case, and a lanthanum-containing
additive case;
[0015] FIG. 8 is a graph of fuel cell voltage against time at fixed
current density and gas flows for each of a reference case, a
coated interconnect case, and a coated interconnect case with a
calcium-containing additive; and
[0016] FIG. 9 is a graph of fuel cell voltage against time at fixed
current density and gas flows for a coated interconnect case with a
lanthanum- and calcium-containing additive.
DETAILED DESCRIPTION OF THE INVENTION
[0017] Embodiments described herein include materials that may be
used as a selective chromium filter in a solid oxide fuel cell
(SOFC) stack and/or system operating in a temperature range of 300
to 850.degree. C. Additionally, such filters may also be used in
solid oxide electrolyzers, reversible solid oxide cells, gas
purification membrane devices such as an oxygen transport membrane,
and/or any device that incorporates a ceramic or cermet electrode
that may suffer performance degradation from chromium vapor species
in the temperature range of 300 to 1000.degree. C.
[0018] In embodiments, a fuel cell stack that has an interconnect
between a first fuel cell and a second fuel cell is provided with a
contact layer coated with a chromium-getter material. The fuel cell
stack may be useful for reducing chromium contamination of a fuel
cell. In some embodiments, the fuel cell stack may be a solid oxide
fuel cell. In other embodiments, different types of fuel cell
stacks may be provided. Turning to FIG. 1, a portion of a fuel cell
stack 100 in an exploded view is shown. FIG. 2 shows the cross
section of an embodiment of the fuel cell stack along the line II.
in FIG. 1. A single fuel cell 110 includes an anode 112 supported
structure having a thin electrolyte 114 and cathode 116. A single
fuel cell stack repeating layer includes fuel cell 110 and an
interconnect 118, which may be a monolithic plate having
flow-directing ribs 120 as shown in FIG. 1. Ribs 120 may assist in
providing an even distribution of airflow across the entire surface
of cathode 116 between air intake and exhaust manifolds of the
stack. Cathode 116 may include a composite material, which includes
a noble metal such as palladium and a ceramic, such as yttrium
stabilized zirconium, as described in co-owned U.S. Pat. No.
6,420,064, the contents of which are incorporated herein by
reference, for all purposes, as if fully set forth herein.
Depending on the embodiment, cathode design may also be in
accordance with U.S. Pat. No. 7,802,698 and/or U.S. Pat. No.
7,190,568, which are incorporated herein by reference for all
purposes, as if fully set forth herein. In some embodiments,
cathode 116 may be a purely ceramic-based cathode. A contact layer
122 may be disposed between cathode 116 and interconnect 118 by
applying contact layer 122 material to one or both of cathode 116
and/or the face of interconnect 118 during assembly of the fuel
cell stack.
[0019] The fuel cell stack may also have a similar or different
contact layer disposed between anode 112 and interconnect 118. In
many embodiments, interconnect 118 may be a source of chromium
within the fuel cell stack. Interconnect 118 and/or any other
portion of the fuel cell stack may also have a protective coating
to mitigate chromium poisoning. Such a coating may include
manganese cobalt oxide spinel phases.
[0020] In some embodiments, the contact layer 122 may have a
thickness of between about 20 .mu.m and about 525 .mu.m. Contact
layer 122 may also include at least two outer layers and a central
layer. The central layer may include electrically conductive
materials. In these or other embodiments, the central layer may
have a porosity of between about 25% and about 70% or between about
30% and about 50%. The central layer may have a thickness of
between about 10 .mu.m and about 250 .mu.m.
[0021] In some embodiments, the outer contact layers may include
fine conductive particles while the central layer may include
coarse conductive particles. In these or other embodiments, the
conductive particles in either or both the fine and coarse layers
may include conductive perovskites. Fine conductive particles may
be particles with diameters less than about 2 .mu.m or between
about 0.3 .mu.m and about 1.1 .mu.m. Coarse particles may include
particles that are, on average, at least one and a half times the
average particle diameter of the fine particles, and/or greater
than about twice the average diameter of the fine particles. The
coarse particles may have average diameters greater than about 1
.mu.m and/or greater than about 1.5 .mu.m.
[0022] In some embodiments, contact layer 122 may be applied in the
form of a contact paste material. As shown in FIG. 3, via a SEM
photograph of an example fuel cell, a contact paste material may be
applied in a multilayer configuration (302, 304, 306). In these or
other embodiments, contact paste may be applied in three layers in
which outer layer 302 adheres to a fuel cell cathode 308 and outer
layer 304 adheres to the interconnect 310. The central layer 306
may have coarse particles sandwiched between the outer layers 302
and 304. An electrolyte 314 may be disposed between cathode 308 and
anode 312.
[0023] In these or other embodiments, cathode 308 may be a ceramic
fuel cell electrode, and outer layer 302 may not be present such
that central layer 306 may be directly adjacent to the cathode 308.
In some embodiments, electrolyte 314 may be a single layer (e.g.
yttria stabilized zirconia), or a bilayer electrolyte (e.g.
gadolinia doped ceria adjacent to cathode 308 and yttria stabilized
zirconia adjacent to this layer).
[0024] In one embodiment, contact layer 122 may include a
chromium-getter material. In some embodiments, contact layer 122
may have pores, and at least a portion of the chromium-getter
material may be disposed within at least a portion of the pores.
The chromium-getter materials may be included as a powder (e.g.,
calcium carbonate and/or lanthanum oxide) and such powder may be
substituted for some of the ceramic powder otherwise present in
contact layer 122 (e.g., substituting calcium carbonate for
perovskite powder). The chromium-getter material may be less than
about 50% by volume of the contact layer, or it may be less than
about 33% by volume of the contact layer. In these or other
embodiments, the chromium-getter material may be about 20% by
volume of contact layer 122.
[0025] Contact layer 122 may have an inorganic material volume. The
inorganic material volume is defined as the volume of the contact
layer minus the volume of the pores and the volume of any organic
material in the contact layer. The chromium-getter material may be
between about 15% and about 33%, between about 10% and 33%, or
between about 1% and about 50% by volume of the inorganic material
volume of the contact layer after heat treatment in the range of
600 to 850.degree. C.
[0026] In some embodiments, the chromium-getter material may
include lanthanum oxide, lanthanum carbonate, or calcium carbonate.
The chromium-getter material may also include barium oxide, lithium
oxide, or sodium oxide. In these or other embodiments, the
chromium-getter material may include barium carbonate, lithium
carbonate, or sodium carbonate. The chromium-getter material may
also include mixtures of these or different compounds, such as
inorganic carbonates, nitrates, hydroxides, or acetates. The
carbonates, nitrates, hydroxides, and acetates may include
lanthanum, barium, calcium, lithium, or sodium in embodiments. In
some embodiments, the chromium-getter material may lower the
conductivity of the contact layer, but any potential decrease in
conductivity may be offset by slower degradation of the electrode
due to the chromium-getter reducing chromium contamination of the
cathode and/or other portions of the fuel cell.
[0027] In these or other embodiments, inorganic carbonates may
include hydrogen carbonates. The inorganic carbonate may react with
chromium such that the inorganic carbonate captures chromium atoms
at an atomic percent ratio of cation to chromium of between about 1
and about 1.7 to 1. Barium carbonate, calcium carbonate, and
lanthanum carbonate may absorb or react with volatile chromium
species at atomic percent ratios of cation to chromium up to 1:1.
The inorganic carbonate may be lanthanum carbonate, calcium
carbonate, lithium carbonate, sodium carbonate, sodium hydrogen
carbonate, and/or barium carbonate. The inorganic oxide may include
a cation that captures chromium atoms at an atomic percent ratio of
cation to chromium of between about 1 and about 1.7 to 1. The
chromium-getter material may comprise lanthanum, barium, calcium,
lithium, sodium, and,/or oxides thereof. The compounds described
herein, as part of the fuel cell stack, may help reduce chromium
contamination in the fuel cell.
[0028] In these or other embodiments, a method of forming a
chromium-getter contact layer and fuel cell may be provided. This
method may help reduce chromium contamination and improve fuel cell
performance. The method may include applying a first layer to the
fuel cell electrode or a fuel cell interconnect. The first layer
may include a perovskite material. The first layer may also include
lanthanum cobalt nickel oxide (LCN) particles, and/or lanthanum
cobalt oxide (LC) particles. The LCN particles may have an average
particle size of about 1.0 .mu.m with about 50% of the particles
falling in the range of about 0.5 .mu.m to about 1.1 .mu.m. The
layer of LCN particles may be less than about 25 .mu.m thick and
may or may not be sintered.
[0029] The method may also include applying a second layer to the
first layer. The second layer may be applied by screen printing
onto the first layer and drying thereafter. The second layer may
have LCN particles with an average particle size of between about
1.5 .mu.m and about 3 .mu.m. The majority of the particles may fall
in the range of between about 1 .mu.m and about 10 .mu.m. This
second layer may be referred to as the coarse LCN layer, cLCN
layer, and/or the stress relief layer.
[0030] In embodiments, a pore-forming material may be added to the
second layer, and this addition may result in the second layer
including pores after formation. Chromium-getter material may be
disposed within the pores of the second layer. In these or other
embodiments, a third layer of LCN particles may be screen printed
onto the second layer. The multiple layers may provide better
long-term cell stability by providing a sacrificial fracture layer
in the central layer, which helps absorb expansion mismatches
during thermal cycling and long-tern operation. The fracture layer,
which may contain a chromium-getter material, may also absorb
chromium vapors. The chromium-getter material may include any of
the compounds previously discussed herein. Although the fracture
layer may absorb chromium, such absorption may not restrict airflow
to the cathode due to the high porosity of the layer.
[0031] The fuel cell stack may be part of a fuel cell system. FIG.
4 shows one possible fuel cell system 400 with a solid oxide fuel
cell stack 402. Solid oxide fuel cell stack 402 may be fuel cell
stack 100 in FIGS. 1 and 2. Solid oxide fuel cell stack 402 along
with an electrical startup heater 404 may be part of a stack module
406. Solid oxide fuel cell stack 402 may include a stack manifold,
which may distribute gases to the stack.
[0032] Stack module 406 may be connected to a hot balance of plant
416. Stack module 406 may be in a stack hot box. The stack hot box
may be an insulated box that includes a stack module and most or
all of hot balance of plant 416. Input streams into hot balance of
plant 416 may include a natural gas inlet 418. Natural gas inlet
418 may provide input gases, including hydrogen, for solid oxide
fuel cells stack 402. Natural gas may also be combusted in a start
burner 420. An ambient air inlet 422 may provide ambient air,
including oxygen, to solid oxide fuel cell stack 402. A water inlet
424 may provide water for hot balance of plant 416. Hot balance of
plant 416 may include other components, including an air heat
exchanger 426, a fuel heat exchanger 428, a pre reformer 430, a
recycle cooler 432, and an afterburner 434. Hot balance of plant
416 may also include hot system piping to connect various
components. Hot balance of plant 416 may be connected to a heat
recovery and exhaust unit operation 436.
[0033] FIG. 5 shows one possible method 500 of the invention for
reducing Chromium contamination of components in a fuel cell.
Reducing chromium contamination of components in a fuel cell may
improve the performance of a fuel cell through increased runtime
and/or higher cell voltage. At step 502, a substrate may be
provided. The substrate may be an inert substrate and may include
alumina. The substrate may be coated with a chromium-getter
material, which may be any of the compounds previously discussed
herein. The chromium-getter material may be in pellet form, powder
form, or any other form including these compounds. The coating
process may cause the chromium-getter material to become bonded to
the substrate through covalent, ionic, or other bonds. Thus, the
coating may be more firmly attached to the substrate.
[0034] At step 504, method 500 may include disposing the coated
substrate in a solid oxide fuel cell stack or system. In some
embodiments, the coated substrate may be disposed in a stack
manifold, hot system piping, and/or a stack hot box of an SOFC
system. In these or other embodiments, the coated substrate may
also be located in the air flow stream of an SOFC interconnect or
any air flow channels of a solid oxide fuel cell. In some
embodiments, it may be desirable to place the coated substrate at
any location in an SOFC system that reaches a temperature of above
about 300.degree. C. The coated substrate may assist in capturing
chromium species from stainless steel or other components found in
the SOFC stack and/or system. In some embodiments, the method may
also include placing the chromium-getter material as a stand-alone
component (without a substrate) in the same or other locations
within a solid oxide fuel cell stack or system. In some cases, the
chromium-getter material may be disposed without a substrate in a
column or other component. Such a column or component may be packed
with powder or pellets of the chromium-getter material. By
disposing the coated substrate with a chromium-getter material in
the locations discussed herein, the chromium-getter material may
help reduce chromium contamination and improve the performance of a
fuel cell.
EXAMPLE 1
[0035] Several oxide powders (manganese, zinc, cobalt, copper, tin,
and nickel oxides) were tested in a tube furnace for their ability
in capturing chromium. Chromium oxide powder was placed in a
crucible with a piece of porous stainless steel on top. The oxide
powders were placed on top of the porous stainless steel. The tests
were performed at 750.degree. C. for 1000 hours in flowing air with
10% humidity. After testing, the oxide powders were weighed to
determine mass changes and energy dispersive x-ray spectroscopy
(EDX) analysis was done to see if any chromium species were
absorbed on the powders. However, no chromium was detected in the
tested powders.
EXAMPLE 2
[0036] Several oxide powders (lanthanum, copper, manganese, tin,
zinc, and cobalt oxides) were tested in a tube furnace for their
ability to capture chromium. Chromium pieces, not chromium oxide
powder, were placed in a crucible with a piece of porous stainless
steel on top. The oxide powders were placed on top of the porous
stainless steel. The tests were performed at 750.degree. C. for
1000 hours in flowing air with 10% humidity. After testing, the
oxide powders were weighed to determine mass changes and EDX
analysis was done to see if any chromium species were absorbed on
the powders. Only the lanthanum oxide sample showed chromium
species on the surface in this example. Areas of the sample with
chromium were yellowish color and contained up to 20 to 25 atomic
percent of chromium compared with lanthanum. This example shows
that while lanthanum oxide may be a chromium-getter material, not
all inorganic oxides can be used as chromium-getter materials.
EXAMPLE 3
[0037] Several powders were tested in a tube furnace for their
ability to capture chromium. These powders included barium
carbonate, strontium carbonate, calcium carbonate, 20 mol %
gadolinia doped ceria, neodymium oxide, and magnesium oxide.
Chromium pieces, not chromium oxide powder, were placed in a
crucible with a piece of porous stainless steel on top. The powders
were placed on top of the porous stainless steel. The tests were
performed at 750.degree. C. for 1000 hours in flowing air with 10%
humidity. After testing, the powders were weighed to determine mass
changes and EDX analysis was done to see if any chromium species
were absorbed on the powders. Barium carbonate and calcium
carbonate showed the best ability to capture chromium in this
example. The 20 mol % gadolinia doped ceria and magnesium oxide did
not capture any chromium species. Neodymium oxide changed color on
the surface (indicating chromium capture) but EDX analysis could
not be performed because of low conductivity even after coating the
sample with gold.
[0038] The morphology of barium carbonate and calcium carbonate
changed after the 1000 hours test. The new compounds appeared
denser. Reacted areas showed a different morphology indicating
different amounts of chromium captured. Barium:chromium ratios of
1.7:1 were found. Calcium:chromium ratios of 1:1 were found. These
tests demonstrate that compounds with atoms from the same group of
the periodic table (e.g., calcium, barium, magnesium) may not all
be effective chromium-getter materials.
EXAMPLE 4
[0039] Barium carbonate powder was blended with cLCN in contact
paste and used in single-cell tests with cathode humidity. Barium
carbonate replaced cLCN in the paste formulation at a ratio of 20%
v/v of the cLCN content. Details of this formulation, with
component amounts in weight percent, are shown in the third line of
Table 1. Results of the test are shown in FIG. 6. The cell degraded
quickly when 10% cathode humidity was introduced. Although the SEM
shows the top surface of the cathode layer becoming denser after
testing as a result of the absorption of chromium species, no or
very little chromium was detected underneath the dense surface of
the contact paste with EDX. On the surface, barium may have reacted
with chromium to form large oxide particles, such as BaCrO.sub.4 or
other chromites, that may have blocked or significantly reduced gas
flow to the cathode. Such reduced gas flow may be the result of
chromium or other species physically absorbing within pores
themselves. The shortage or lack of detectable chromium underneath
the surface may be the result of some other blocking mechanism.
TABLE-US-00001 TABLE 1 LCN coarse Lanthanum Calcium Barium Ethyl
Fish powder Graphite oxide carbonate carbonate Terpineol cellulose
oil Total 54.7 7.4 11.8 0.0 0.0 22.2 1.5 2.5 100.0 60.3 8.2 0.0 5.4
0.0 22.2 1.5 2.5 100.0 57.8 7.8 0.0 0.0 8.3 22.2 1.5 2.5 100.0 58.9
8.0 5.5 1.5 0.0 22.2 1.5 2.5 100.0 45.8 8.3 15.7 4.1 0.0 22.2 1.5
2.5 100.0 58.9 8.0 2.9 4.1 0.0 22.2 1.5 2.5 100.0
EXAMPLE 5
[0040] In this example, chromium-getter materials were incorporated
into the coarse LCN paste during the standard screen-printing ink
process by triple-roll milling or high shear mixing of the
ingredients in the desired quantities. Possible screen-printing ink
formulations for lanthanum oxide and calcium carbonate additions
are listed in Table 1. All values in the table are in weight
percent.
EXAMPLE 6
[0041] Cell voltage was measured against time for various single
cell tests. In these tests, baseline materials systems were
compared to cells with calcium- or lanthanum-containing additives
in the central contact layer. Chromium-getter material was added in
the amount of 20% v/v of the inorganic content of the contact
layer, and all tests were performed in 10% humidity to give a
higher than expected concentration of volatile chromium species.
FIG. 7 shows the cell test comparison for a reference cell with no
chromium-filter material and cells with calcium or lanthanum
addition. The reference case (labeled as 101768 reference) over 428
hours showed the equivalent of a 21.64% drop in voltage over 1,000
hours. The calcium test (labeled as 101833 Ca-cLCN and the second
line in Table 1) over 2,000 hours showed the equivalent of a 7.64%
drop in voltage over 1.000 hours, while the lanthanum test
(labelled as 101838 La-cLCN and the first line in Table 1) over
1450 hours showed the equivalent of a 3.6% drop in voltage over
1,000 hours. Thus, the reference case showed a decline in cell
voltage that was both earlier and faster than tests with calcium-
or lanthanum-containing additives. The calcium test was performed
separately from lanthanum test. These tests showed that the
addition of calcium or lanthanum in this example was effective at
maintaining cell performance, potentially by capturing chromium
species.
[0042] Incorporating lanthanum oxide into the cLCN layer also led
to a significant reduction in degradation rate and had a much
longer period with no increase in degradation when 10% humidity was
introduced compared with dry air. FIG. 7 shows lanthanum
outperformed calcium in this example.
EXAMPLE 7
[0043] Calcium-containing additives were added to the cLCN contact
paste and tested in conjunction with a coated cathode jig and
tested. For the purposes of this test, the coated cathode, jig
represents a stack interconnect and uses the same material used in
an SOFC stack. FIG. 8 shows the effect of using a coated cathode
jig (interconnect) alone and the improvement seen when using
calcium carbonate in addition to a coating, As shown in FIG. 8, the
430SS interconnect coated with cobalt (labeled as 101777 w coated
430) showed slower and less degradation than the uncoated reference
case (labeled as 101768 reference). The addition of a
calcium-containing additive along with a different coated
interconnect (labeled as 101843 Ca-cLCN w coated ZMG) resulted in
even slower and less degradation. In this example, the interconnect
is ZMG 232 G10, a stainless steel with a slightly different
composition from 430SS and may have better resistance to high
temperature oxidation than 430SS. Over the testing duration, no
degradation was seen in a coated interconnect with a
calcium-containing additive, with the test showing the equivalent
of a -0.4% drop in voltage over 1000 hours.
EXAMPLE 8
[0044] A mixture of calcium carbonate and lanthanum oxide additives
were added to the cLCN contact paste and tested in conjunction with
a ZMG 232 G10 cathode jig coated with cobalt. FIG. 9 shows the
effect of a coated cathode jig with the formulation in line 4 of
Table 1. The ZMG 232 G10 jig coated with cobalt degraded slightly
slower than the 430SS jig coated with cobalt. For the ZMG 232 G10
jig coated with cobalt and the calcium carbonate and lanthanum
oxide additive, the test showed the equivalent of a 0.55% drop in
voltage per 1000 hours operation.
EXAMPLE 9
[0045] After a cathode contact layer of a single cell was tested at
10% humidity for 1600 hours, the cathode contact layer was analyzed
by SEM and EDX. The central contact layer had a 20% v/v calcium
carbonate additive. The results of the EDX analysis are shown in
Table 2, with all results in atomic percent. The EDX analysis
showed that calcium had a near 1:1 atomic ratio with chromium after
testing, indicating it may be an effective chromium-getter.
TABLE-US-00002 TABLE 2 Spectrum O Ca Cr Co Ni La 1 79.04 8.68 8.78
0.98 0.66 1.86 2 71.33 12.51 13.50 0.64 0.62 1.40
[0046] Having described several embodiments, it will be recognized
by those of skill in the art that various modifications,
alternative constructions, and equivalents may be used without
departing from the spirit of the invention. Additionally, a number
of well-known processes and elements have not been described in
order to avoid unnecessarily obscuring the present invention.
Additionally, details of any specific embodiment may not always be
present in variations of that embodiment, or may be added to other
embodiments.
[0047] Where a range of values is provided, it is understood that
each intervening value, to the tenth of the unit of the lower limit
unless the context clearly dictates otherwise, between the upper
and lower limits of that range is also specifically disclosed. Each
smaller range between any stated value or intervening value in a
stated range and any other stated or intervening value in that
stated range is encompassed. The upper and lower limits of these
smaller ranges may independently be included or excluded in the
range, and each range where either, neither, or both limits are
included in the smaller ranges is also encompassed within the
invention, subject to any specifically excluded limit in the stated
range. Where the stated range includes one or both of the limits,
ranges excluding either or both of those included limits are also
included.
[0048] As used herein and in the appended claims, the singular
forms "a", "an", and "the" include plural referents unless the
context clearly dictates otherwise. Thus, for example, reference to
"a method" includes a plurality of such methods and reference to
"the layer" includes reference to one or more layers and
equivalents thereof known to those skilled in the art, and so
forth. The term "about" when used to modify a numerical value
indicates a level of precision around that numerical value as
expected by a skilled artisan The invention has now been described
in detail for the purposes of clarity and understanding. However,
it will be appreciated that certain changes and modifications may
be practice within the scope of the appended claims.
* * * * *