U.S. patent application number 15/396730 was filed with the patent office on 2017-05-25 for solid oxide fuel cells, electrolyzers, and sensors, and methods of making and using the same.
This patent application is currently assigned to FCET, Inc.. The applicant listed for this patent is FCET, Inc.. Invention is credited to Leonid V. Budaragin, Mark A. Deininger, Paul D. Fisher, Mikhail Pozvonkov, D. Morgan Spears, II.
Application Number | 20170146481 15/396730 |
Document ID | / |
Family ID | 49840829 |
Filed Date | 2017-05-25 |
United States Patent
Application |
20170146481 |
Kind Code |
A1 |
Pozvonkov; Mikhail ; et
al. |
May 25, 2017 |
Solid Oxide Fuel Cells, Electrolyzers, and Sensors, and Methods of
Making and Using the Same
Abstract
The present invention provides solid oxide fuel cells, solid
oxide electrolyzer cells, solid oxide sensors, components of any of
the foregoing, and methods of making and using the same. In some
embodiments, a solid oxide fuel cell comprises an air electrode (or
cathode), a fuel electrode (or anode), an electrolyte interposed
between the air electrode and the fuel electrode, and at least one
electrode-electrolyte transition layer. Other embodiments provide
novel methods of producing nano-scale films and/or surface
modifications comprising one or more metal oxides to form
ultra-thin (yet fully-dense) electrolyte layers and electrode
coatings. Such layers and coatings may provide greater ionic
conductivity and increased operating efficiency, which may lead to
lower manufacturing costs, less-expensive materials, lower
operating temperatures, smaller-sized fuel cells, electrolyzer
cells, and sensors, and a greater number of applications.
Inventors: |
Pozvonkov; Mikhail;
(Cumming, GA) ; Deininger; Mark A.; (Roswell,
GA) ; Fisher; Paul D.; (Landis, NC) ;
Budaragin; Leonid V.; (Moscow, RU) ; Spears, II; D.
Morgan; (Atlanta, GA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
FCET, Inc. |
Roswell |
GA |
US |
|
|
Assignee: |
FCET, Inc.
Roswell
GA
|
Family ID: |
49840829 |
Appl. No.: |
15/396730 |
Filed: |
January 2, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14093445 |
Nov 30, 2013 |
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15396730 |
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12420457 |
Apr 8, 2009 |
8623301 |
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14093445 |
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61043566 |
Apr 9, 2008 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
G01N 27/406 20130101;
Y02P 70/50 20151101; C25B 1/46 20130101; H01M 8/126 20130101; Y02E
60/366 20130101; H01M 2300/0094 20130101; H01M 8/1246 20130101;
H01M 2008/1293 20130101; Y02P 70/56 20151101; C25B 13/04 20130101;
H01M 8/0232 20130101; C25B 1/10 20130101; C25B 9/08 20130101; G01N
27/40 20130101; H01M 2300/0077 20130101; H01M 8/1253 20130101; Y02E
60/525 20130101; Y02E 60/50 20130101; G01N 27/4073 20130101 |
International
Class: |
G01N 27/407 20060101
G01N027/407; C25B 13/04 20060101 C25B013/04; C25B 1/46 20060101
C25B001/46; C25B 1/10 20060101 C25B001/10; H01M 8/1253 20060101
H01M008/1253; H01M 8/126 20060101 H01M008/126 |
Claims
1. A sensor for at least one analyte, comprising at least one metal
oxide made by a process comprising: applying at room temperature a
liquid composition to a substrate that can be adapted to function
as an electrode in the sensor, the liquid composition comprising at
least one metal compound, at least one nanoparticle having an
average size of 50-100 nm, and optionally at least one carboxylic
acid, and converting at least some of the at least one metal
compound to at least one metal oxide on the substrate; and wherein
the sensor is adapted to function by passing at least one ion
through the at least one metal oxide to detect at least one
analyte.
2. The sensor of claim 1, wherein the at least one analyte is
chosen from O.sub.2, CO, CO.sub.2, H.sub.2, NO.sub.x, SO.sub.x,
H.sup.+, K.sup.+, Na.sup.+, and glucose.
3. The sensor of claim 1, wherein the at least one analyte is
oxygen.
4. The sensor of claim 1, wherein the at least one metal compound
comprises at least one zirconium compound and at least one yttrium
compound.
5. The sensor of claim 1, further comprising a transition layer
between the substrate and the at least one metal oxide.
6. The sensor of claim 5, wherein the transition layer has a
thickness less than about 10 nm.
7. The sensor of claim 1, wherein the substrate comprises at least
one catalytic material.
8. The sensor of claim 7, wherein the at least one catalytic
material is chosen from platinum, palladium, rhodium, nickel,
cerium, gold, silver, zinc, lead, ruthenium, rhenium, and
combinations thereof.
9. The sensor of claim 1, wherein the at least one metal oxide
comprises a plurality of metal oxide layers on the substrate.
10. The sensor of claim 9, wherein the plurality of metal oxide
layers comprise at least one compositional gradient.
11. The sensor of claim 10, wherein the at least one compositional
gradient comprises substrate material, and the plurality of metal
oxide layers comprise a greater concentration of substrate material
in a region proximal to the substrate than in a region distal to
the substrate.
12. The sensor of claim 1, wherein the sensor is a lambda
sensor.
13. The sensor of claim 1, further comprising a second electrode
separated from the substrate by the at least one metal oxide.
14. The sensor of claim 13, wherein the second electrode comprises
at least one catalytic material.
15. The sensor of claim 14, wherein the at least one catalytic
material is chosen from platinum, palladium, rhodium, nickel,
cerium, gold, silver, zinc, lead, ruthenium, rhenium, and
combinations thereof.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims benefit of priority under 35
U.S.C. .sctn.120 and is a continuation of U.S. Non-Provisional
patent application Ser. No. 14/093,445, filed on Nov. 30, 2013 and
entitled, "Solid Oxide Fuel Cells, Electrolyzers, and Sensors, and
Methods of Making and Using the Same," now allowed; which claims
benefit of and is a continuation of U.S. Non-Provisional patent
application Ser. No. 12/420,457, filed on Apr. 8, 2009, now U.S.
Pat. No. 8,623,301 B1, entitled, "Solid Oxide Fuel Cells,
Electrolyzers, and Sensors, and Methods of Making and Using the
Same;" which claims benefit under 35 U.S.C. .sctn.119(e) to U.S.
Provisional Patent Application No. 61/043,566 filed on Apr. 9,
2008, and entitled, "Solid Oxide Fuel Cells, Electrolyzers, and
Sensors, and Methods of Making and Using the Same." Each of the
foregoing applications is incorporated herein by reference in its
entirety.
FIELD OF THE INVENTION
[0002] The present invention relates to electrical energy systems
such as fuel cells, electrolyzer cells, and sensors, and, in
particular, to solid oxide fuel cells, solid oxide electrolyzer
cells, solid oxide sensors, and components of any of the
foregoing.
BACKGROUND OF THE INVENTION
[0003] Solid oxide fuel cells, otherwise known as ceramic fuel
cells, present an environmentally friendly alternative to
mainstream electrical energy production processes involving the
combustion of fossil fuels. Solid oxide fuel cells enable the
catalytic conversion of chemical energy stored in hydrogen into
electrical energy without the concomitant release of greenhouse
gases. The generation of electrical current by a solid oxide fuel
cell using a hydrogen fuel results in the production of water as
opposed to the production carbon dioxide, nitrous oxides, and/or
sulfur dioxides associated with the combustion of fossil fuels.
[0004] In addition to hydrogen, solid oxide fuel cells are operable
to function on a wide variety of fuel sources. Fuel sources in
addition to hydrogen include hydrocarbons such as methane, natural
gas, and diesel fuel. Hydrocarbon fuel sources are reformed into
hydrogen for use with solid oxide fuel cells. Hydrocarbon reforming
can be administered prior to entry into the fuel electrode or can
be administered at the fuel electrode of a solid oxide fuel cell.
The ability to function on a wide variety of fuels distinguishes
solid oxide fuel cells from other fuel cells which lack the ability
to operate on various fuels. Furthermore, the ability of solid
oxide fuel cells to administer hydrocarbon feedstock reformation
frees such fuel cells from the limitations associated with hydrogen
production and distribution.
[0005] Currently, solid oxide fuel cells operate at high
temperatures ranging from about 800.degree. C. to 1000.degree. C.
As a result of high operating temperatures, solid oxide fuel cells
require the use of exotic materials which can withstand such
operating temperatures. The need for exotic materials greatly
increases the costs of solid oxide fuel cells, making their use in
certain applications cost-prohibitive. Moreover, high operating
temperatures often induce grain growth in the various component
layers of a solid oxide fuel cell, including the electrolyte. Grain
growth can reduce ion conductivity through the electrolyte thereby
degrading the efficiency of the solid oxide fuel cell. High
operating temperatures additionally exacerbate stresses caused by
differences in coefficients of thermal expansion between component
layers of a solid oxide fuel cell. Differences in coefficients of
thermal expansion between component layers of a solid oxide fuel
cell can lead to cracking at interfaces of the layers as well as
within the layers. Differences in coefficients of thermal expansion
between the air electrode and the electrolyte, for example, can
lead to cracking at the electrode-electrolyte interface and within
the electrode and/or electrolyte.
[0006] In certain circumstances, a solid oxide fuel cell can
operate "in reverse" to electrolyze water into hydrogen gas and
oxygen gas by inputting electrical energy. In other circumstances,
a solid oxide electrolyzer cell can be designed primarily for use
as a hydrolyzer, generating hydrogen and oxygen for later use. In
still other circumstances, an electrolyzer cell can be used for
other purposes, such as extraction of metal from ore and
electroplating. In conventional electrolyzers, electrical energy is
lost in the electrolysis reaction driving the diffusion of ions
through the electrolyte and across the distance between the
electrodes. Also, the ability to conduct electrolysis at higher
temperatures would improve the efficiency of the electrolysis.
However, at higher temperatures, electrolyzers face similar thermal
stresses and cracking caused by differences in coefficients of
thermal expansion between component layers of the solid oxide
electrolyzer cell. Accordingly, better matching of coefficients of
thermal expansion is desired for electrolyzer cells.
[0007] A lambda sensor is a device typically placed in the exhaust
stream of an internal combustion engine to measure the
concentration of oxygen. That measurement allows regulation of the
richness or leanness of the fuel/air mixture flowing into the
engine. If the fuel/air stream contains too much oxygen, the
quantity .lamda. is greater than 1, and the mixture is too lean. If
the fuel/air stream contains too little oxygen, then .lamda.<1
and the mixture is too rich. .lamda. equals 1, the ideal situation,
when the mixture contains a stoichiometrically equivalent
concentration of oxygen and hydrocarbon to allow for complete
combustion. A lambda sensor positioned in the exhaust stream
detects the amount of oxygen in the combustion products, thereby
providing feedback regarding richness or leanness. Lambda sensors
and other sensors rely on the diffusion of oxygen anions (O.sup.2-)
and other ions through barrier materials in ways similar to the
manner in which oxygen anions diffuse through a solid electrolyte
of a solid oxide fuel cell. Moreover, given the high operating
temperature of lambda sensors and similar devices, sensors face
thermal stresses, cracking, and delamination issues similar to
those facing fuel cells and electrolyzers. Accordingly, embodiments
of the present invention provide for improved sensor technology by
addressing mismatching of coefficients of thermal expansion, among
other reasons.
SUMMARY
[0008] In view of the foregoing problems and disadvantages
associated with the high operating temperatures of solid oxide
cells, it would be desirable to provide solid oxide cells that can
demonstrate lower operating temperatures. In addition, providing
solid oxide cells and components that better tolerate higher
temperatures would be advantageous. Moreover, the efficiency losses
due to the thickness of electrolytes make thinner electrolytes
desirable.
[0009] As used herein, "solid oxide cell" means any electrochemical
cell that contains at least one metal oxide, and refers to, for
example, solid oxide fuel cells, solid oxide electrolyzer cells,
cells that can operate as a fuel cell and an electrolyzer cell, and
solid oxide sensors. One method of lowering operating temperatures
of solid oxide cells is to increase the efficiency of oxygen
transport across the solid electrolyte. Since oxygen transport
efficiency decreases linearly with electrolyte thickness, the
thinner the electrolyte layer, the higher the efficiency of oxygen
transport. Thus, the thinner the electrolyte, the higher the
operating efficiency of the solid oxide cell will be. A thinner
electrolyte layer also can lower the operating temperature of a
solid oxide cell.
[0010] Some embodiments of the present invention provide
electrolyte in the form of an ultra-thin yet fully dense film
having a thickness less than 1 micron. A thickness less than 1
.mu.m represents a reduction in thickness of 2-3 orders of
magnitude over many existing ceramic electrolyte constructions.
[0011] In addition, by lowering the operating temperature of a
solid oxide cell, less exotic and easier-to-fabricate materials can
be utilized in the construction of the cell leading to lower
production costs. Thus, some embodiments of the present invention
provide solid oxide cells and components thereof employing simpler,
less-expensive materials than the current state of the art. For
example, if the operating temperature of a solid oxide cell can be
lowered, then metals can be used for many different components such
as electrodes and interconnects. At these lower operating
temperatures, metals have more desirable mechanical properties,
such as higher strength, than ceramics. In addition, this higher
strength can allow metal components also to have a higher degree of
porosity. Current ceramic electrode materials allow for porosity
levels in the range of 30% to 40%. Incorporating higher porosity
levels in ceramic materials renders them too structurally weak to
support cell construction. However, through the use of certain
metals or metal carbides, the porosity of an electrode can be
provided in the higher range of 40% to 80% and yet retain
sufficient mechanical strength for cell construction. Some
embodiments of the present invention provide an electrode having a
porosity ranging from about 40% to about 80%.
[0012] Lower production costs in addition to lower operating
temperatures provide the opportunity for solid oxide cells to find
application in a wider variety of fields. Additionally, lower
operating temperatures reduce degradative processes such as those
associated with grain growth and variances in coefficients of
thermal expansion between dissimilar component layers of the cell.
Accordingly, some embodiments provide means and methods for
reducing at least one degradation process in a solid oxide
cell.
[0013] Further embodiments of the present invention apply conformal
nano-scale surface treatments to porous metal substrates so that
the pore size can be reduced to either micron- or
submicron-dimensions; thus, the increase in the active surface area
of an electrode component results in an increase in the efficiency
of the electrode by as much as an order of magnitude.
[0014] Still other embodiments produce a desirable surface
catalytic effect. For example, by using a process of some
embodiments of the present invention, thin films of metal oxides
and pure metals (or other metal compounds) can be formed on the
exposed pore surfaces of electrodes to produce more chemically
active sites at triple phase boundaries where either fuel-gas (as
in the case of the anode electrode) or gaseous oxygen (as in the
case of the cathode electrode) come into contact with the solid
(yet porous) electrodes in a fuel cell.
[0015] Other embodiments provide methods of making solid oxide
cells and components thereof. Current methods of making solid oxide
fuel cells involve the sintering of ceramic and/or metal powders.
High sintering temperatures during fabrication of various
components, such as the electrolyte, can result in excessive grain
growth as well as compound problems associated with variances in
coefficients of thermal expansion. Furthermore, sintering provides
little control over the ability to vary the composition of an
electrolyte or electrode as a function of the thickness of the
electrolyte or electrode.
[0016] In one embodiment, the present invention provides a solid
oxide fuel cell comprising an air electrode, a fuel electrode, an
electrolyte interposed between the air electrode and the fuel
electrode, and at least one electrode-electrolyte transition layer.
In other embodiments of the present invention, an
electrode-electrolyte transition layer is interposed between an
electrode and the electrolyte. An electrode-electrolyte transition
layer, in some embodiments, is interposed between the air electrode
and the electrolyte. In other embodiments, an electrode-electrolyte
transition layer is interposed between the fuel electrode and the
electrolyte. In a further embodiment, a solid oxide fuel cell
comprises a first electrode-electrolyte transition layer interposed
between the air electrode and electrolyte and a second
electrode-electrolyte transition layer interposed between the fuel
electrode and the electrolyte. In one embodiment, a solid oxide
fuel cell does not comprise an electrode-electrolyte transition
layer, and an abrupt interface exists between an electrode and
electrolyte. Even other embodiments provide more than one
electrode-electrolyte transition layer.
[0017] Moreover, in order to reduce problems and disadvantages
associated with variances in coefficients of thermal expansion
between electrodes and electrolytes of solid oxide cells and to
increase ionic conductivities, electrolytes of certain embodiments
of the present invention comprise compositional gradients. An
electrolyte of a solid oxide cell, in one embodiment, comprises a
region proximal to an electrode and a region distal to the
electrode, wherein the region proximal to the electrode comprises a
greater amount of electrode material than the region distal to the
electrode. An electrode, for example, comprises
La.sub.1-xSr.sub.xMnO.sub.3 [lanthanum strontium doped manganite
(LSM)]. The region of the electrolyte proximal to the electrode
comprises greater amounts of LSM in comparison with the region of
the electrolyte distal from the electrode.
[0018] An electrolyte of a solid oxide cell, in another embodiment,
comprises a plurality of metal oxide layers. Metal oxide layers of
the electrolyte proximal to an electrode comprise a greater amount
of electrode material than metal oxide layers of the electrolyte
distal to the electrode. An electrode, for example, comprises
La.sub.1-xSr.sub.xMnO.sub.3 [lanthanum strontium doped manganite
(LSM)]. Metal oxide layers of an electrolyte proximal to the
electrode, in one embodiment, comprise greater amounts of LSM in
comparison with metal oxide layers of the electrolyte distal from
the electrode.
[0019] Incorporating greater amounts of electrode material in an
electrolyte region or electrolyte layers proximal or adjacent to
the electrode in a solid oxide cell establishes a compositional
gradient in the electrolyte. Such a compositional gradient can
permit an electrolyte region or electrolyte layers proximal to the
electrode to demonstrate a coefficient of thermal expansion which
better matches the coefficient of thermal expansion of the
electrode. As a result, disparities in coefficients of thermal
expansion between the electrode and the electrolyte can be reduced
or eliminated leading to a more stable solid oxide cell.
[0020] In view of this, in some embodiments, a solid oxide cell
comprises a first electrode comprising a first material and an
electrolyte comprising a first region proximal to the first
electrode and a second region distal to the first electrode,
wherein the first region of the electrolyte comprises a greater
amount of the first material than the second region of the
electrolyte.
[0021] In another embodiment, a solid oxide cell comprises a first
electrode comprising a first material and an electrolyte comprising
a plurality of layers of an electrolyte material, wherein layers of
the electrolyte material proximal or adjacent to the first
electrode further comprise greater amounts of the first material of
the first electrode than layers of the electrolyte distal or spaced
apart from the first electrode.
[0022] In order to reduce problems and disadvantages associated
with variances in coefficients of thermal expansion between
electrode and electrolytes of solid oxide cells, electrodes, in
some embodiments of the present invention, comprise compositional
gradients. An electrode, in one embodiment, comprises a region
proximal to the electrolyte and a region distal to the electrolyte,
wherein the region proximal to the electrolyte comprises a greater
amount of electrolyte material than the region of the electrode
distal to the electrolyte. In another embodiment, an electrode of a
solid oxide cell comprises a plurality of layers. Layers of the
electrode proximal to the electrolyte comprise greater amounts of
electrolyte material than layers of the electrode distal to the
electrolyte. A solid oxide cell, in some embodiments, comprises a
first electrode comprising a plurality of layers of a first
material and an electrolyte comprising an electrolyte material
disposed on the first electrode, wherein layers of the first
material proximal or adjacent to the electrolyte further comprise
greater amounts of the electrolyte material than layers of the
first material distal or spaced apart from the electrolyte.
[0023] In addition to variances in coefficients of thermal
expansion, some of the solid oxide cells of the present invention
also address fuel, air, and other reactant delivery mechanisms by
providing electrodes comprising porosity and optionally, porosity
gradients. For example, electrodes of solid oxide fuel cells may be
porous in order to allow the ingress of air and fuel to the
electrolyte and the egress of other gases produced or not consumed
by the fuel cell. In one embodiment, a solid oxide cell comprises a
solid electrolyte disposed on a first electrode, the first
electrode comprising a first region proximal to the solid
electrolyte and a second region distal to the electrolyte, wherein
the first region has a porosity less than the second region.
Alternatively, in another embodiment, the first region of the
electrode has a porosity that is greater than the second region of
the electrode. One embodiment provides a porous electrode having a
first region adapted to be proximate to electrolyte having pores of
approximately 200 nm in diameter, and a second region adapted to be
distal to the electrolyte having pores of approximately 10-15 .mu.m
in diameter. The two regions can be any suitable thickness. For
example, the first region can be 200 nm thick, and the second
region can be about 1 .mu.m thick. The thicknesses of the two (or
more, if desired) regions balance the mechanical strength of the
porous electrode with the movement of reactant and product gases
through the electrode. If the electrode is too thin, then it may be
too brittle. If it is too thick, movement of gas through the
electrode may hinder cell operation.
[0024] Moreover, in some embodiments, a solid oxide cell comprises
a first electrode comprising a plurality of layers of a first
material and a solid electrolyte disposed on the first electrode,
wherein layers of the first material proximal to the solid
electrolyte have porosities less than layers of the first material
distal to the solid electrolyte. Alternatively, in other
embodiments, layers of the first material proximal to the solid
electrolyte have porosities greater than layers of the first
material distal to the solid electrolyte.
[0025] In another aspect, some embodiments of the present invention
provide electrodes operable in solid oxide cells as well as other
applications. Electrodes of the present invention, in some
embodiments, are resistant to harsh environments and various
chemical species which can foul the electrodes, such as sulfur. In
one embodiment, the present invention provides an electrode
comprising a substrate comprising a first material, a coating
comprising at least one layer of at least one metal oxide disposed
on the substrate, and a substrate-coating transition layer
interposed between the substrate and the coating. As used herein,
"disposed on the substrate" need not mean, for example, that the at
least one layer of at least one metal oxide directly contacts the
substrate. Moreover, "interposed between the substrate and the
coating" does not necessarily mean that the transition layer is
inserted between the substrate and the coating after the coating is
formed. Forming those embodiments is described in more detail
below. In some embodiments, an electrode comprises a plurality of
layers of at least one metal oxide disposed on the substrate. An
electrode, in one embodiment, is an anode. An electrode, in another
embodiment, is a cathode. In some embodiments, the metal oxide
coating of an electrode can protect the electrode substrate from
corrosion and/or degradation.
[0026] Electrodes, according to some embodiments, further comprise
at least one catalytic material. Catalytic materials can comprise
transition metals including, but not limited to, platinum,
palladium, rhodium, nickel, cerium, gold, silver, zinc, lead,
ruthenium, rhenium, or mixtures thereof. Catalytic materials, in
some embodiments, are disposed in one or a plurality of metal oxide
layers coating the substrate. The combination of a metal oxide with
pure metals or alloys, in some embodiments, produces a cermet.
Electrodes of solid oxide fuel cells further comprising catalytic
materials can function as fuel reformers converting hydrocarbon
fuels into hydrogen for subsequent use in the solid oxide fuel
cell. Moreover, electrodes further comprising catalytic materials
can function as fuel reformers upstream and independent from solid
oxide fuel cells.
[0027] Electrodes comprising catalytic materials can optionally
demonstrate compositional gradients based on the distribution of
the catalytic materials in the plurality of metal oxide layers. In
one embodiment, an electrode comprises a substrate and a plurality
of metal oxide layers disposed on the substrate, wherein metal
oxide layers proximal to the substrate comprise greater amounts of
catalytic material than metal oxide layers distal to the substrate.
Moreover, in another embodiment, metal oxide layers distal to the
substrate comprise greater amounts of catalytic material than metal
oxide layers proximal to the substrate.
[0028] In another aspect, the present invention provides
interconnects operable to be used in solid oxide cells as well as
other applications. Interconnects of the present invention, in some
embodiments, are resistant to harsh environments and chemical
species which can degrade the interconnects. In one embodiment, the
present invention provides an interconnect comprising a substrate
comprising a first material, a coating composition comprising at
least one layer of metal oxide, and a substrate-coating transition
layer interposed between the substrate and the coating. In some
embodiments, a coating composition comprises a plurality of metal
oxide layers. One or a plurality of metal oxide coatings can assist
in protecting a metallic or ceramic interconnect substrate from
degradative conditions and/or chemical species.
[0029] Additionally, in order to reduce problems and disadvantages
associated with variances in coefficients of thermal expansion
between interconnects and electrodes of solid oxide cells,
interconnects, in some embodiments of the present invention,
comprise one or more compositional gradients. An interconnect, in
one embodiment, comprises a region proximal to a cathode of a solid
oxide cell and a region distal to the cathode, wherein the region
proximal to the cathode has a greater amount of cathode material
than the region of the interconnect distal from the cathode.
Moreover, in another embodiment, an interconnect comprises a region
proximal to an anode of a solid oxide cell and a region distal to
the anode, wherein the region proximal to the anode has a greater
amount of anode material than the region of the interconnect distal
from the anode.
[0030] In another embodiment, an interconnect comprises a substrate
coated with a plurality of metal oxide layers. Layers of the
interconnect proximal to the cathode comprise greater amounts of
cathode material than layers of the interconnect distal from the
cathode. Moreover, in another embodiment, layers of the
interconnect proximal to the anode comprise greater amounts of
anode material than layers of the interconnect distal from the
anode.
[0031] Some embodiments of the present invention provide materials
in which more than one concentration gradient is present. For
example, in a material A between two other materials B and C, the
material A can exhibit one independent concentration gradient of
the material B, and a second independent concentration gradient of
material C. Gradients of various other ingredients and properties,
such as porosity, also can be exhibited in those and other
embodiments of the present invention. Such independent gradients
can be formed, in some embodiments, by successive disposition of
layers of material A, wherein each successive layer contains the
desired amount of material B, material C, and porosity, for
example.
[0032] In another aspect, the present invention provides methods of
making solid oxide cells. In one embodiment, a method of making a
solid oxide cell comprises providing a first electrode, applying a
metal compound composition to the first electrode, and converting
at least some of the metal compound composition to a metal oxide
composition. In some embodiments, the metal compound composition is
fully converted to a metal oxide composition. In some embodiments,
the metal compound composition comprises at least one metal
carboxylate, at least one metal alkoxide, at least one metal
.beta.-diketonate, or a combination thereof.
[0033] Converting a metal compound composition, according to some
embodiments of the present invention, comprises exposing the metal
compound composition to an environment operable to convert the at
least one metal salt to at least one metal oxide. Environments
operable to convert metal compounds to metal oxides, in some
embodiments, demonstrate conditions sufficient to vaporize and/or
decompose the compounds and precipitate metal oxide formation. In
one embodiment, an environment operable to convert metal compounds
to metal oxides comprises a heated environment. A metal salt of a
carboxylic acid, for example, can be exposed to an environment
heated to a temperature operable to evaporate the carboxylic acid
and induce formation of the metal oxide. In some embodiments, the
environment is heated to a temperature greater than about
400.degree. C. In other embodiments, the environment is heated to a
temperature ranging from about 400.degree. C. to about 650.degree.
C. In some embodiments, the environment is heated to a temperature
of up to about 425.degree. C. or up to about 450.degree. C. In
still other embodiments, the environment is heated to a temperature
ranging from about 650.degree. C. to about 800.degree. C., or from
about 800.degree. C. to about 1000.degree. C.
[0034] In some embodiments, an environment operable to convert
metal compounds to metal oxides is free or substantially free of
oxygen. In other embodiments, an environment operable to convert
metal compounds to metal oxides comprises oxygen.
[0035] In another embodiment, a method of making a solid oxide cell
comprises providing a first electrode and depositing at least one
electrolyte layer on the first electrode, wherein depositing at
least one electrolyte layer comprises applying a metal compound
composition to the first electrode, and converting at least some of
the metal compound composition to at least one metal oxide.
[0036] In some embodiments, a plurality of electrolyte layers is
stacked on the first electrode. A method of producing a solid oxide
cell, in one embodiment, comprises providing a first electrode and
stacking a plurality of electrolyte layers on the first electrode,
wherein each layer of electrolyte is stacked on a preceding layer
by applying a metal compound composition to the preceding layer.
The metal compound composition is subsequently converted to at
least one metal oxide.
[0037] In addition to solid oxide cells, the present invention
provides methods of making electrodes. In one embodiment, a method
of making an electrode comprises providing a substrate and
depositing at least one metal oxide layer on the substrate wherein
depositing comprises applying a metal compound composition to the
substrate, and converting at least some of the metal compound
composition to at least one solid oxide composition. In some
embodiments, the metal compound composition is fully converted to a
metal oxide.
[0038] In some embodiments, a plurality of metal oxide layers is
deposited on the substrate. In one embodiment, for example, a
method of making an electrode comprises depositing a plurality of
metal oxide layers on the substrate, wherein each layer of metal
oxide is deposited on a preceding layer by applying a metal
compound composition to the preceding layer. The metal compound
composition is subsequently converted to at least one metal oxide
to form another layer of metal oxide.
[0039] Metal compound compositions, in some embodiments of
electrode production methods, further comprise one or more
catalytic materials. Catalytic materials, in such embodiments,
comprise transition metals including, but not limited to, platinum,
palladium, rhodium, nickel, cerium, gold, silver, zinc, lead,
ruthenium, rhenium, or mixtures thereof. In other embodiments,
metal compound compositions further comprise nanoparticles,
powders, or both, operable to alter the pore structure and/or
porosity of the metal oxide resulting from the conversion of the
metal compound composition. Nanoparticles, in some embodiments,
comprise metal oxide nanoparticles. Nanoparticles, as used herein,
have an average size less than about 1 .mu.m, while powders are
those particulate materials having an average size equal to or
greater than 1 .mu.m.
[0040] In another aspect, the present invention provides methods of
making interconnects. In one embodiment, a method of making an
interconnect comprises providing a substrate and depositing at
least one metal oxide layer on the substrate wherein depositing
comprises applying metal compound composition to the substrate, and
converting at least some of the metal compound composition to at
least one metal oxide, thereby forming the at least one metal oxide
layer. In some embodiments, the metal compound composition is fully
converted to at least one metal oxide.
[0041] In some embodiments, a plurality of metal oxide layers are
deposited on the substrate. In one embodiment, for example, a
method of making an interconnect comprises depositing a plurality
of metal oxide layers on the substrate, wherein each layer of metal
oxide is deposited on a preceding layer by applying a metal
compound composition to the preceding layer. The metal compound
composition is subsequently converted to at least one metal oxide
to form a layer.
[0042] In another aspect, the present invention provides methods of
increasing the ionic conductivity of a solid electrolyte. A method
of increasing the ionic conductivity of a solid electrolyte, in
some embodiments, comprises increasing the number of grain
boundaries in the solid electrolyte, wherein increasing the number
of grain boundaries comprises forming a plurality of
nanocrystalline grains comprising an electrolyte material. In some
embodiments of the present invention, an electrolyte material
comprises one or more metal oxides. Forming a plurality of metal
oxide nanocrystalline grains comprises applying a metal compound
composition to a substrate, and converting at least some of the
metal compound composition to a plurality of metal oxide
nanocrystalline grains.
[0043] In another aspect, the present invention provides methods of
increasing the number of triple phase boundaries in a solid oxide
cell comprising providing an electrolyte comprising a plurality of
metal oxide nanocrystalline grains. Providing an electrolyte
comprising a plurality of nanocrystalline grains, in some
embodiments, comprises applying a metal compound composition to a
substrate, and converting at least some of the metal compound
composition to a plurality of metal oxide nanocrystalline grains.
In some embodiments, the metal compound composition is fully
converted into a plurality of metal oxide nanocrystalline grains.
In one embodiment, the substrate comprises an electrode of a solid
oxide cell.
[0044] In a further aspect, the present invention provides methods
of reducing differences in coefficients of thermal expansion
between an electrode and an electrolyte of a solid oxide cell. In
one embodiment, a method of reducing differences in coefficients of
thermal expansion between an electrode and an electrolyte comprises
interposing an electrode-electrolyte transition layer between the
electrode and the electrolyte. Interposing an electrode-electrolyte
transition layer between the electrode and the electrolyte
comprises applying an electrolyte composition comprising a metal
compound composition to the electrode, and converting at least some
of the liquid metal compound to at least one metal oxide.
[0045] In some embodiments of methods of the present invention, a
metal compound comprises a transition metal compound. In other
embodiments, a metal compound comprises a rare earth metal
compound. In a further embodiment, metal compound compositions
comprise a plurality of metal compounds. In one embodiment, a
plurality of metal compounds comprises at least one rare earth
metal compound and at least one transition metal compound. In still
other embodiments, the at least one metal compound comprises metal
ions that are the same or different, and ligands that are the same
or different. In some embodiments, those ligands are chosen from
one or more carboxylates, one or more alkoxides, one or more
.beta.-diketonates, and combinations thereof. Moreover, in
embodiments of methods of the present invention, metal compound
compositions can comprise liquid metal compound compositions, solid
metal compound compositions, vapor metal compound compositions, or
combinations thereof. In one embodiment, a liquid metal carboxylate
composition comprises an excess of the liquid carboxylic acid used
to form the metal carboxylate salt. In another embodiment, a liquid
metal compound composition comprises a solvent including, but not
limited to, organic solvents such as benzene, toluene, xylene,
chloroform, dichloromethane, or mixtures thereof. In some
embodiments, solid metal compound compositions comprise metal
compound powders. In a further embodiment, a vapor metal compound
composition comprises at least one gas phase metal compound
operable to condense on a substrate prior to conversion to at least
one metal oxide. In one embodiment, a metal compound composition
comprises at least one gel including, but not limited to, a
sol-gel, hydrogel, or a combination thereof.
[0046] In yet another aspect, the present invention provides a
method of generating electric current from a solid oxide fuel cell
that comprises at least one air electrode (or cathode); at least
one fuel electrode (or anode); and, at least one electrolyte layer
interposed between the at least one air electrode and the at least
one fuel electrode. This tri-layer construction, in some
embodiments, also includes at least one electrode-electrolyte
transition layer where fuel is in contact with the fuel electrode
(or anode); and also, another electrode-electrolyte transition
layer where gaseous oxygen is in contact with the air electrode (or
cathode). The middle layer comprises the electrolyte, which can be
solid, non-porous, and fully-dense. The middle electrolyte layer
serves as a barrier that prevents premature mixing of the fuel gas
(on the anode side of the cell) with the gaseous oxygen (on the
cathode side of the cell). Other embodiments provide cells
comprising more than one cathode electrode, and/or more than one
anode electrode. Still other embodiments provide a plurality of
cells, wherein the cells are connected in series, in parallel, or a
combination thereof.
[0047] While not intending to be bound by theory, the solid oxide
fuel cell of certain embodiments produces electricity as follows.
Molecular diatomic oxygen is reduced to oxygen anions at the air
electrode (or cathode). Diatomic hydrogen reacts with these oxygen
anions after the oxygen anions have been transported through the
electrolyte layer and to the anodic side of the tri-layer
arrangement. When the hydrogen fuel and the oxygen anions form
water, for example, as steam, electrons are also a product of this
reaction. The electrons produced by the reaction can then flow
around an external circuit (through an electrically-conductive
interconnect). These electrons (released when water is formed)
further become available for the repeated reduction of molecular
diatomic oxygen into oxygen anions at the air electrode or
cathode.
[0048] In this way, the production of both electric current and
water is a continuous process--as long as hydrogen (from some
hydrogen-containing fuel source) and oxygen continue to be supplied
to the opposite sides of the cell (separated from each other by the
electrolyte--as described above).
[0049] In some embodiments, the fuel comprises pure hydrogen. But,
in other embodiments, the fuel comprises a hydrocarbon, such as a
fossil fuel that contains hydrogen--but that also contains other
elements such as carbon.
[0050] A solid oxide fuel cell has a unique ability among the
various types of fuel cells to operate on either pure hydrogen or
(with minor alterations) other types of fossil fuels and
hydrocarbons. In embodiments wherein the fuel is a hydrocarbon,
methods of generating electrical current further comprise
"reforming" (or releasing hydrogen from hydrocarbon) the
hydrocarbon fuel internally at the fuel electrode (or anode).
[0051] In another aspect, some embodiments provide a solid oxide
electrolyzer cell or a component thereof comprising at least one
metal oxide, wherein the at least one metal oxide has been made by
a process comprising: [0052] applying at least one metal compound
to a substrate, and [0053] converting at least some of the at least
one metal compound to the at least one metal oxide.
[0054] Still other embodiments provide a sensor or a component
thereof comprising at least one metal oxide, wherein the at least
one metal oxide has been made by a process comprising: [0055]
applying at least one metal compound to a substrate, and [0056]
converting at least some of the at least one metal compound to the
at least one metal oxide.
[0057] Additional embodiments provide a method for detecting at
least one analyte, comprising
providing at least one sensor for the at least one analyte, wherein
the at least one sensor comprises at least one metal oxide made by
a process comprising: [0058] applying at least one metal compound
to a substrate, and [0059] converting at least some of the at least
one metal compound to the at least one metal oxide; and passing at
least one ion through the at least one metal oxide to detect the at
least one analyte.
[0060] These and other embodiments are described in greater detail
in the detailed description which follows.
BRIEF DESCRIPTION OF THE DRAWINGS
[0061] FIG. 1 is a micrograph at approximately 2
million.times.magnification that illustrates a thin film of
yttria-stabilized zirconia ("YSZ": a material that can be used to
produce ceramic electrolytes in solid oxide cells) with an
interlayer (106) between the pure YSZ thin film (102) and the pure
stainless steel (grade 304) of the substrate (104). The mixed
YSZ-oxide & substrate interlayer (106) appears between the
lower steel substrate layer (104) and the upper YSZ-oxide layer
(102). As used herein, "interlayer" and "transition layer" are used
interchangeably.
[0062] FIG. 2 illustrates a solid oxide fuel cell according to one
embodiment of the present invention.
DETAILED DESCRIPTION
[0063] The present invention provides solid oxide cells and methods
of making and using the same.
[0064] In some embodiments, solid oxide cells of the present
invention demonstrate lower operating temperatures. Lowering the
operating temperature of solid oxide cells enables the cells to be
constructed from less expensive materials thereby rendering their
production more cost friendly. In addition to cost savings, solid
oxide cells having lower operating temperature can find application
in a wider variety of fields. Furthermore, lower operating
temperatures reduce stress on the individual components of the cell
thereby reducing the onset of degradation pathways (such as
cracking or delamination) that result from variances in
coefficients of thermal expansion among dissimilar types of
materials that comprise the component layers--or that result from
excessive grain growth arising from exposure to high process
("sintering") or operating temperatures.
[0065] Furthermore, it would be desirable to lower the operating
temperature of a solid oxide cell so that metals (instead of
ceramics) can be used for electrode substrate construction. Metals
generally have a higher level of mechanical strength, so they can
also have a higher porosity and yet maintain an adequate degree of
structural strength that is needed for the solid oxide cell's
integrity.
[0066] Current ceramic electrode materials allow for porosity
levels in the range of 30% to 40%. When these porosity levels are
exceeded, structural (i.e. mechanical) strength becomes too weak to
support cell construction.
[0067] However, by using certain types of metals or metal carbides,
the porosity of an electrode can be increased to a range of 40% to
80%. And yet, these porous metallic materials still retain
sufficient mechanical strength to allow cell construction.
[0068] It would additionally be desirable to apply conformal
nano-scale surface treatments or thin films onto these porous
metallic materials. These conformal surface treatments reduce the
pore-size to either micron- or submicron-sized dimensions. With the
addition of these surface treatments, the active surface area of an
electrode component can increase the efficiency of the thus-treated
electrode by as much as an order of magnitude.
[0069] This is particularly true if the surface treatments or thin
films also exhibit a surface catalytic effect in addition to the
efficiency improvements of modified surface area noted above. The
catalytic effect of the surface treatments or thin films, in some
embodiments, can be adjusted to enhance operating efficiency of the
solid oxide cell and, thus, to lower operating temperature. In
other embodiments, solid oxide cells of the present invention
demonstrate greater tolerance for high operating temperatures. That
greater tolerance enables such cells to be constructed from less
expensive materials, and may increase service lifetime. The
increased tolerance for high operating temperatures stems from the
greater matching of coefficients of thermal expansion available to
at least some embodiments of the present invention.
[0070] In still other embodiments, solid oxide cells exhibit
increased operational efficiency due to decreased electrolyte
thicknesses. Thinner electrolytes allow for lower energy losses due
to ion diffusion through the electrolyte. Some embodiments of the
present invention include a solid oxide electrolyte having a
thickness of 100-1000 times thinner than ceramic electrolytes made
according to conventional methods.
I. Solid Oxide Cells Useful as Fuel Cells
[0071] In one embodiment, the present invention provides a solid
oxide fuel cell comprising an air electrode, a fuel electrode, an
electrolyte interposed between the air electrode and the fuel
electrode, and at least one electrode-electrolyte transition layer.
In some embodiments of the present invention, an
electrode-electrolyte transition layer is interposed between an
electrode and the electrolyte. An electrode-electrolyte transition
layer, in some embodiments, is interposed between the air electrode
and the electrolyte. In other embodiments, an electrode-electrolyte
transition layer is interposed between the fuel electrode and the
electrolyte. In a further embodiment, a solid oxide fuel cell
comprises a first electrode-electrolyte transition layer interposed
between the air electrode and the electrolyte and a second
electrode-electrolyte transition layer interposed between the fuel
electrode and the electrolyte.
[0072] Turning now to components that can be included in solid
oxide fuel cells, solid oxide fuel cells of the present invention
comprise an air electrode. The air electrode of a solid oxide fuel
cell operates as a cathode to reduce oxygen molecules thereby
producing oxygen anions for subsequent transport through the
electrolyte. In some embodiments, an air electrode comprises p-type
semiconducting oxides such as lanthanum manganite (LaMnO.sub.3).
Lanthanum manganite can be doped with rare earth elements, such as
strontium, cerium, and/or praseodymium to enhance conductivity. In
one embodiment, an air electrode comprises
La.sub.1-xSr.sub.xMnO.sub.3 [lanthanum strontium doped manganite
(LSM)]. In another embodiment, an air electrode comprises lanthanum
strontium ferrite or lanthanum strontium cobaltite or a combination
thereof.
[0073] Air electrodes, according to some embodiments of the present
invention, are porous. In one embodiment, an air electrode has a
porosity ranging from about 5% to about 30%. In another embodiment,
an air electrode has a porosity ranging from about 10% to about 25%
or from about 15% to about 20%. In a further embodiment, an air
electrode has a porosity greater than about 30%. An air electrode,
in some embodiments, has a porosity ranging from about 30% to about
60% or from about 40% to about 80%. In one embodiment, an air
electrode has a porosity greater than about 80%.
[0074] A lower operating temperature allows non-ceramic materials
such as metals and metal carbides to be used. Since these materials
generally possess higher levels of mechanical or structural
strength at the lower operating temperatures, they can have higher
levels of porosity than either ceramics (such as the LSM that can
be used for cathodes) or cermets (such as mixtures of nickel and
zirconia that can be used for anodes).
[0075] Metallic materials also tend to be easier to fabricate; and,
they do not require high process (or `sintering`) temperatures.
Such high process temperatures can result in detrimental
micro-structural grain growth, which can occur both in previously
processed ceramic and in the metallic components of the fuel
cell.
[0076] Additionally, films for surface modification of air
electrodes can have any desired thickness. In one embodiment, a
thin film applied to an air electrode has a thickness ranging from
about 10 nm to about 1 micron. In another embodiment, an
air-electrode-film has a thickness ranging from about 10 nm to
about 50 nm, from about 50 nm to about 750 .mu.m, from about 50 nm
to about 500 nm, from about 500 nm to about 500 .mu.m, from about 1
.mu.m to about 350 .mu.m, or from about 10 .mu.m to about 200
.mu.m. In a further embodiment, an air electrode has a thickness
ranging from about 50 .mu.m to about 100 .mu.m.
[0077] These thin films are used in some embodiments to modify the
surface of porous air electrodes (cathodes) that, themselves, can
be composed of porous metals or metal carbides. By using a
non-ceramic porous material (such as a metal or metal carbide) as
the body (or substrate) onto which a thin film is applied, many of
the adverse structural and processing conditions of ceramic
materials (such as high sintering temperatures) can be avoided. In
addition, the operating efficiency of a solid oxide fuel cell
comprised of these metallic and metallic carbide materials can also
be significantly enhanced.
[0078] In addition to an air electrode, a solid oxide fuel cell
comprises a fuel electrode. A fuel electrode, in some embodiments,
comprises one or more metal oxides combined with one or a plurality
of catalytic materials. Catalytic materials, as provided herein,
comprise transition metals including, but not limited to, platinum,
palladium, rhodium, nickel, cerium, gold, silver, zinc, lead,
ruthenium, rhenium, or mixtures thereof. In one embodiment, a fuel
electrode comprises zirconia (ZrO.sub.2) combined with Ni.
Yttria-stabilized zirconia (YSZ),
Zr.sub.(1-x)Y.sub.xO.sub.[2-(x/2)], for example, can be combined
with Ni to produce a Ni--YSZ fuel electrode. Catalytic materials,
in some embodiments, are incorporated into metal oxide compositions
of fuel electrodes in an amount ranging from about 0.5 to about 10
weight percent. In other embodiments, catalytic materials are
incorporated into metal oxide compositions of fuel electrodes in an
amount less than about 5 weight percent, less than about 0.5 weight
percent, or greater than about 10 weight percent.
[0079] Fuel electrodes, according to some embodiments of the
present invention, are porous. In one embodiment, a fuel electrode
has a porosity ranging from about 5% to about 40%. In another
embodiment, a fuel electrode has a porosity ranging from about 10%
to about 30% or from about 15% to about 25%. In a further
embodiment, a fuel electrode has a porosity greater than about 40%.
A fuel electrode, in some embodiments, has a porosity ranging from
about 40% to about 80%. In still other embodiments, a fuel
electrode has a porosity greater than about 80%.
[0080] Additionally, the films used to treat the surface of fuel
electrodes (or anodes) can have any desired thickness. In one
embodiment a fuel electrode film has a thickness ranging from about
10 nm to about 1 micron. In another embodiment, the thickness of
the film applied to the surfaces of a fuel electrode has a
thickness ranging from about 50 nm to about 2 microns; or, from
about 500 nm to about 1.5 microns; or, from about 750 nm to about 1
micron.
[0081] An electrolyte for solid oxide cells, for example interposed
between the fuel electrode and the air electrode in some
embodiments, comprises one or a plurality of layers of one or more
metal oxides. In some embodiments, metal oxides suitable for
electrolyte layers comprise zirconium oxides combined with various
transition and/or rare earth metals, including, but not limited to,
scandium, yttrium, erbium, ytterbium, europium, gadolinium, or
dysprosium, or combinations thereof. In one embodiment, a metal
oxide suitable for one or more layers of an electrolyte comprises
zirconium oxide (ZrO.sub.2) or yttria-stabilized zirconia (YSZ)
Zr.sub.(1-x)Y.sub.xO.sub.[2-(x/2)], x=0.08-0.11. In another
embodiment, a suitable electrolyte metal oxide comprises
scandia-stabilized zirconia (SSZ)
Zr.sub.(1-x)Sc.sub.xO.sub.[2-(x/2)], x=0.09-0.11. Additional
suitable electrolyte zirconium compounds comprise zirconium
silicate (ZrSiO.sub.4), Zr.sub.0.85Ca.sub.0.15 O.sub.1.85 or
3ZrO.sub.22 CeO.sub.2+10% CaO.
[0082] In another embodiment, metal oxides of an electrolyte
comprise cerium oxides of the general formula
Ce.sub.(1-x)M.sub.xO.sub.(2-.delta.). In some embodiments M is
samarium or gadolinium to produce CeO.sub.2--Sm.sub.2O.sub.3 or
CeO.sub.2--Gd.sub.2O.sub.3.
[0083] Additional metal oxides suitable for electrolyte layers of
solid oxide cells of the present invention comprise perovskite
structured metal oxides. In some embodiments, perovskite structured
metal oxides comprise lanthanum gallates (LaGaO.sub.3). Lanthanum
gallates, in some embodiments, are doped with alkaline earth metals
or transition metals, or combinations thereof. In another
embodiment, a perovskite structure metal oxide comprises lanthanum
strontium gallium magnesium oxide (LSGM)
La.sub.(1-x)Sr.sub.xGa.sub.(1-y)Mg.sub.yO.sub.(3-.delta.),
x=0.10-0.20, y=0.15-0.20.
[0084] In a further embodiment, metal oxides suitable for
electrolyte layers comprise brownmillerites, such as barium indiate
(Ba.sub.2In.sub.2O.sub.6), non-cubic oxides such as lanthanum
silicate, neodymium silicate, or bismuth based oxide, or
combinations thereof.
[0085] Layers of an electrolyte, in some embodiments, are
constructed independently and without reference to one another. As
a result, a plurality of electrolyte layers can display the same
compositional construction or different compositional
constructions. Thus, for example, a compositional gradient can be
introduced into an electrolyte in the following manner. An
electrode material is chosen, such as, for example, LSM. An
electrolyte material is also chosen, such as, for example, YSZ. To
make the YSZ electrolyte, as will be further explained below, metal
compounds containing yttrium and zirconium and possibly others will
be applied to the surface of the electrode and converted into the
corresponding metal oxides. This application and conversion can be
repeated to form more than one layer of electrolyte on the
electrode. Accordingly, metal compounds corresponding to the
material of the electrode can be included in the applying step
forming the first layers of the electrolyte. In this example,
lanthanum compounds, strontium compounds, manganese compounds, and
combinations thereof can be applied to the electrode surface along
with the yttrium compounds and zirconium compounds, to impart a
concentration of species corresponding to the electrode material in
the electrolyte. As subsequent layers of electrolyte are formed,
the concentration or amount of lanthanum compounds, strontium
compounds, manganese compounds, and combinations thereof applied to
the electrode (more accurately, to the previously-formed layer(s)
of electrolyte) are decreased. If desired, the concentration of
species corresponding to the electrode material in the electrolyte
can be decreased to zero in subsequent layers of electrolyte, or
the compositional gradient can assume any desired profile across
the electrolyte. The species corresponding to the electrode
material in the electrolyte can be any suitable species in any
suitable dispersion, such as, for example, metal oxides, ionic
impurities, solid solutions, distinct domains, and the like.
[0086] Electrolyte layers of solid oxide cells, according to some
embodiments of the present invention, comprise a plurality of
nanocrystalline grains, the nanocrystalline grains comprising one
or more of the metal oxides that are suitable for use as an
electrolyte in a solid oxide cell. In some embodiments, the
nanocrystalline grains have an average size of less than about 50
nm. In other embodiments, nanocrystalline grains of electrolyte
layers have an average size ranging from about 2 nm to about 40 nm
or from about 3 nm to about 30 nm. In another embodiment,
nanocrystalline grains have an average size ranging from about 10
nm to about 25 nm. In a further embodiment, nanocrystalline grains
have an average size less than about 10 nm or less than about 5
nm.
[0087] Electrolytes of solid oxide cells are substantially non
porous, in some embodiments. In one embodiment, an electrolyte has
a porosity less than about 20%. In another embodiment, an
electrolyte has a porosity less than about 15% or less than about
10%. In a further embodiment, an electrolyte has a porosity less
than about 5% or less than about 1%. In one embodiment, an
electrolyte is fully dense meaning that the electrolyte has no
porosity.
[0088] In some embodiments, an electrolyte has a thickness ranging
from about 1 nm to about 1 mm or from about 10 nm to about 500
.mu.m. In other embodiments, an electrolyte has a thickness ranging
from about 50 nm to about 250 .mu.m, from about 100 nm to about 100
.mu.m, or from about 500 nm to about 50 .mu.m. In another
embodiment, an electrolyte has a thickness ranging from about 750
nm to about 10 .mu.m, or from about 1 .mu.m to about 5 .mu.m, or
from about 1.2 .mu.m to about 4 .mu.m, or from about 1.5 .mu.m to
about 2 .mu.m. In a further embodiment, an electrolyte has a
thickness less than about 10 .mu.m or less than about 1 .mu.m. In
one embodiment, an electrolyte has a thickness ranging from about 1
nm to about 100 nm or from about 50 nm to about 100 nm. In still
other embodiments, an electrolyte has a thickness greater than
about 500 .mu.m.
[0089] In some embodiments wherein an electrolyte comprises a
plurality of layers, each layer has a thickness ranging from about
3 nm to about 15 nm, wherein the total thickness of the electrolyte
is the summation of the thicknesses of the individual layers. In
other embodiments, a layer of electrolyte can have a thickness less
than about 3 nm or greater than about 15 nm.
[0090] Materials suitable for use in air electrodes, fuel
electrodes, electrolyzer electrodes, sensors, and/or electrolytes,
in addition to the materials recited hereinabove, can be chosen
from CeO.sub.2--ZrO.sub.2 wherein CeO.sub.2 is about 10-90 weight
percent; yttria-stabilized zirconia (YSZ) wherein yttria is present
in an amount of about 1-50 mol percent; CeO.sub.2--PrO.sub.2
wherein PrO.sub.2 is up to about 50 weight percent;
PrO.sub.2--CeO.sub.2--ZrO.sub.2 wherein PrO.sub.2--CeO.sub.2 is up
to about 90 weight percent; PrO.sub.2--ZrO.sub.2 wherein PrO.sub.2
is 10 to 90 weight percent; scandia-doped zirconia (SSZ) doped with
one or more of Co.sub.3O.sub.4, Bi.sub.2O.sub.3, SiO.sub.2,
TiO.sub.2, Fe.sub.2O.sub.3, NiO, MnO.sub.2, CeO.sub.2, and
Al.sub.2O.sub.3, YSZ doped with one or more of Co.sub.3O.sub.4,
Bi.sub.2O.sub.3, SiO.sub.2, TiO.sub.2, Fe.sub.2O.sub.3, NiO,
MnO.sub.2, CeO.sub.2, and Al.sub.2O.sub.3; CaO stabilized zirconia
doped with one or more of Co.sub.3O.sub.4, Bi.sub.2O.sub.3,
SiO.sub.2, TiO.sub.2, Fe.sub.2O.sub.3, NiO, MnO.sub.2, CeO.sub.2,
and Al.sub.2O.sub.3; mixed LSM and YSZ; and combinations
thereof.
[0091] Oxides of the following elements can be used in embodiments
of air electrodes, fuel electrodes, electrolyzer electrodes,
sensors, and/or electrolytes in some embodiments of the present
invention: lithium, beryllium, sodium, magnesium, aluminum,
silicon, potassium, calcium, scandium, titanium, vanadium,
chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium,
germanium, arsenic, bromine, rubidium, strontium, yttrium,
zirconium, niobium, molybdenum, technetium, ruthenium, rhodium,
palladium, antimony, tellurium, silver, cadmium, indium, tin,
cesium, barium, lanthanum, cerium, praseodymium, neodymium,
promethium, samarium, europium, gadolinium, terbium, dysprosium,
holmium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum,
tungsten, rhenium, osmium, irridium, gold, mercury, thallium, lead,
bismuth, radium, actinium, platinum, thorium, protactinium,
uranium, neptunium, plutonium, americium, berkelium, californium,
einsteinium, fermium, mendelevium, nobelium, lawrencium, or curium.
Oxides containing more than one of the foregoing elements, and
oxides containing elements in addition to the foregoing elements,
also can be used in embodiments of the present invention.
[0092] Moreover, in some embodiments, catalytic metals can be
incorporated into each of the foregoing metal oxide materials in an
amount ranging from about 0.5 to about 10 weight percent. In other
embodiments, catalytic metals can be incorporated in an amount less
than about 5 weight percent.
[0093] In some embodiments of solid oxide cells of the present
invention, an electrode-electrolyte transition layer is interposed
between the electrolyte and the electrode. An electrode-electrolyte
transition layer comprises both electrode and electrolyte
materials. By comprising both electrode and electrolyte materials,
the electrode-electrolyte transition layer, in some embodiments, is
operable to reduce disparities in coefficients of thermal expansion
between the electrode and electrolyte. Reducing such disparities
can have an inhibitory effect on degradative pathways such as
cracking or delamination between the electrode and electrolyte.
Moreover, an electrode-electrolyte transition layer provides
increased stability by anchoring the electrolyte to the electrode.
The electrode-electrolyte transition layer, in some embodiments,
additionally provides a robust base on which to further build an
electrolyte, the electrolyte having thickness less than about 10
.mu.m or less than about 1 .mu.m.
[0094] In some embodiments, an electrode-electrolyte transition
layer has a thickness ranging from about 50 nm to about 100 nm or
from about 20 nm to about 80 nm. In another embodiment, an
electrode-electrolyte transition layer has a thickness ranging from
about 30 nm to about 60 nm or from about 40 nm to about 50 nm. In a
further embodiment, an electrode-electrolyte transition layer has a
thickness less than about 10 nm or greater than about 100 nm.
[0095] FIG. 1 is a micrograph at approximately 2
million.times.magnification illustrating an electrode-electrolyte
transition layer according to one embodiment of the present
invention. In the micrograph, a YSZ electrolyte (102) is disposed
on an electrode substrate (104) made of stainless steel 304. An
electrode-electrolyte interlayer (106) is interposed between the
YSZ electrolyte (102) and the electrode substrate (104).
[0096] In some embodiments, a solid oxide fuel cell comprising an
air electrode, a fuel electrode, an electrolyte interposed between
the air electrode and the fuel electrode, and optionally at least
one electrode-electrolyte transition layer has an operating
temperature less than about 1000.degree. C. or less than about
900.degree. C. In another embodiment, a solid oxide fuel cell of
the present invention has an operating temperature of less than
about 800.degree. C., less than about 700.degree. C., less than
about 600.degree. C., or less than about 500.degree. C. In a
further embodiment, a solid oxide fuel cell of the present
invention has an operating temperature of less than about
300.degree. C.
II. Solid Oxide Cells Useful as Electrolyzers
[0097] Some embodiments of the present invention provide solid
oxide electrolyzer cells or a component thereof comprising at least
one metal oxide. In certain embodiments, the at least one
electrolyzer cell or a component thereof is substantially identical
in manufacture and composition as the fuel cells and components
described above.
[0098] In some of those embodiments of the present invention where
the same cell can function as an electrolyzer cell and alternately
as a fuel cell simply by reversing the flow of electrons, the
cathode of the electrolyzer corresponds to the fuel electrode of
the fuel cell; and the anode of the electrolyzer corresponds to the
air electrode of the fuel cell. Those of ordinary skill in the art
recognize that oxidation occurs at the anode, and reduction occurs
at the cathode, so the name of a given electrode may differ
depending on whether the cell is operating as an electrolyzer or as
a fuel cell.
[0099] In other embodiments, electrons flow in the same direction,
regardless of whether the cell is electrolyzing or producing
electricity. This can be accomplished, for example, by supplying
oxygen anions to a given electrode in electrolysis mode, and
alternately supplying hydrogen to the same electrode in fuel cell
mode. Such an electrode will function as the oxidizing anode in
either mode.
[0100] Accordingly, some embodiments of the present invention
provide a solid oxide electrolyzer cell, comprising at least one
first electrode, at least one second electrode, and at least one
electrolyte interposed between the first electrode and the second
electrode. The cell optionally contains at least one
electrode-electrolyte transition layer, at least one composition
gradient, at least one porosity gradient, or a combination thereof.
In some embodiments, the at least one electrolyte is made by
applying a metal compound composition to a substrate, and
converting at least some of the metal compound composition to at
least one metal oxide.
[0101] The present invention also provides, in some embodiments, a
method for making at least one product, comprising:
providing at least one solid oxide cell comprising at least one
first electrode, at least one second electrode, and at least one
metal oxide interposed between the at least one first electrode and
at least one second electrode; contacting the at least one first
electrode with at least one reactant; and supplying electrical
energy to the at least one first electrode and the at least one
second electrode thereby causing the at least one reactant to
undergo electrochemical reaction to yield the at least one
product.
[0102] The skilled electrochemist will appreciate that a complete
circuit is necessary for electrical energy to cause electrochemical
reaction. For example, at least one ion may traverse the metal
oxide electrolyte to complete the electrical circuit at the second
electrode. Moreover, at least one second product may be formed at
the second electrode due to electrochemical reaction. Therefore,
some embodiments further provide for contacting the at least one
second electrode with at least one second reactant, thereby causing
the at least one second reactant to undergo electrochemical
reaction to yield at least one second product. Contacting an
electrode and supplying electrical energy can occur in any suitable
order. In a continuous process, electrical energy supply is
maintained while additional reactant(s) enter the cell and
product(s) are removed.
[0103] Any suitable reactant can be supplied to an electrode for
electrochemical reaction. Suitable reactants include, but are not
limited to, water such as, for example, pure water, fresh water,
rain water, ground water, salt water, purified water, deionized
water, water containing at least one ionic substance, brine,
acidified water, basified water, hot water, superheated water,
steam, carbon dioxide, carbon monoxide, hydrogen, nitrous oxides,
sulfur oxides, ammonia, metal salts, molten metal salts, and
combinations thereof. Ionic substances include those substances
that release at least one ion when placed in contact with water,
and include, but are not limited to, salts, acids, bases, and
buffers. Reactants, and for that matter, products, can be in any
suitable form, including solid, liquid, gas, and combinations
thereof. Solid reactants and/or solid products lend themselves to
batch processes, although suitable methods for removing a solid
product from a cell can be employed. Fluid reactants and products
can appear in either batch or continuous processes. Optionally,
heat energy is applied to the reactant, the product, at least one
electrode, the at least one metal oxide, the cell, or a combination
thereof.
[0104] Some embodiments provide at least one sacrificial electrode.
A sacrificial electrode itself reacts in the electrolysis process,
and is thereby consumed or rendered unreactive as the reaction
proceeds. For example, a zinc electrode can be consumed in a
suitable solid oxide cell reaction, yielding Zn.sup.2+ and two
electrons per mole of zinc consumed. In another example, an
electrode can become coated and thereby rendered unreactive by
solid product forming on its surface. The unreactive electrode can
be removed from the cell, and the product extracted from the
electrode, or the product can be used on the electrode in another
process. The electrode then can be regenerated, recycled, or
discarded. Alternatively, a sacrificial electrode can be made to
gradually insert into a cell at a rate consistent with the rate at
which the electrode is consumed.
[0105] A reactant undergoing electrochemical reaction can be
oxidized and/or reduced, and chemical bonds may form and/or break.
For example, when water undergoes electrolysis, hydrogen-oxygen
bonds break, H.sup.+ is reduced to H.sup.0, O.sup.2- is oxidized to
O.sup.0, and H.sub.2 and O.sub.2 form, in some circumstances.
Hydrogen peroxide and other species may form in other
circumstances. The skilled artisan will appreciate that many
electrode half reactions can be substituted so that any variety of
anions, cations, and other species may result from electrochemical
reaction.
[0106] In one embodiment, water containing NaCl can be electrolyzed
to form hydrogen gas and NaOH at the cathode, and chlorine gas at
the anode, in the so-called chlor-alkali process:
2NaCl(aq)+2H.sub.2O(l).fwdarw.2NaOH(aq)+Cl.sub.2(g)+H.sub.2(g)
A solid oxide cell arranged to carry out that reaction, in some
embodiments, provides water containing a high concentration of NaCl
(for example, saturated) to a first electrode that will act as an
anode, and provides water to a second electrode that will act as a
cathode. The cell also provides liquid effluent collection to
remove the depleted NaCl solution from the anode, and
NaOH-containing water from the cathode. The cell further provides
gas effluent collection to remove chlorine gas from the anode and
hydrogen gas from the cathode. Optionally, the hydrogen and
chlorine can be subject to electrochemical reaction to release the
electrochemical energy stored by the foregoing electrolysis, or
they can be used for other industrial processes, such as the
synthesis of sodium hypochlorite.
[0107] The present invention also provides methods for storing
electrochemical energy. In some embodiments, at least one reactant
is supplied to at least one electrode of a solid oxide cell, the at
least one reactant undergoes one or more electrochemical reactions
and yields at least one fuel, thereby storing electrochemical
energy. The electrochemical reaction may also yield other products,
such as cations, anions, and other species, some of which may form
at a second electrode of the solid oxide cell that completes an
external circuit. At least one first electrode and at least one
second electrode are separated by at least one metal oxide
electrolyte in the solid oxide cell. The fuel can be subjected to
energy conversion processes such as reverse electrochemical
reaction in a fuel cell or battery, combustion, and the like to
release the stored electrochemical energy.
[0108] In one embodiment, electrochemical energy is stored by
providing a reactant to at least one cathode; reducing the reactant
at the at least one cathode to release at least one anion and at
least one fuel; storing the at least one fuel; transporting the at
least one anion through at least one metal oxide electrolyte to at
least one anode; and oxidizing the at least one anion. Optionally,
the oxidized anion is stored as well, separately from the stored
fuel. Thus, in one embodiment, water in a suitable form is supplied
to a cathode, at which it is reduced to hydrogen (H.sub.2) and
oxygen anion (O.sup.2-); the hydrogen is collected and stored,
while the oxygen anion diffuses through a solid metal oxide
electrolyte to an anode where the oxygen anion is oxidized to
oxygen (O.sub.2). Optionally, in the foregoing non-limiting
example, the oxygen is collected and stored as well.
[0109] When desired, the stored hydrogen can be fed to any suitable
fuel cell, including but not limited to the cell that produced the
hydrogen, and the hydrogen can be oxidized to release the stored
electrochemical energy. Any suitable gas can be fed to the air
electrode of the fuel cell, such as, for example, the
optionally-stored oxygen, other oxygen, other oxygen-containing gas
such as air, and combinations thereof. Alternatively, the stored
hydrogen can be combusted with oxygen to propel a rocket, drive a
piston, rotate a turbine, and the like. In other embodiments, the
stored hydrogen can be used in other industrial processes, such as
petroleum cracking.
[0110] Some embodiments involve those reactants that yield the high
energy materials commonly found in primary (nonrechargeable) and
secondary (rechargeable) batteries. For secondary battery
materials, the low-energy (discharge) state materials may be
produced, since secondary batteries can be charged before first
use. Such materials include, but are not limited to, MnO.sub.2,
Mn.sub.2O.sub.3, NH.sub.4Cl, HNO.sub.3, LiCl, Li, Zn, ZnO,
ZnCl.sub.2, ZnSO.sub.4, HgO, Hg, NiOOH, Ni(OH).sub.2, Cd,
Cd(OH).sub.2, Cu, CuSO.sub.4, Pb, PbO.sub.2, H.sub.2SO.sub.4, and
PbSO.sub.4.
[0111] At least some embodiments of fuel cells described above can
be used to provide electrolyzer cell embodiments of the present
invention. While fuel cell embodiments optionally employ one or
more of fuel supply, air or oxidizer supply, interconnects, and
electrical energy harvesting means (e.g., wires forming a circuit
between the fuel and air electrodes' interconnects), electrolyzer
cell embodiments optionally employ one or more of reactant supply,
fuel collection, interconnects, and electrical energy supply.
Optionally, electrolyzer cell embodiments also provide collection
means for other products in addition to fuel. The reactant supply
provides any suitable reactant for electrolysis. Fuel collection,
in some embodiments, involves collecting hydrogen for storage and
later use. Storage vessels, metal hydride technology, and other
means for storing hydrogen are known in the art. Fuel collection,
in other embodiments, involves collection of, for example,
carbon-coated electrodes for later oxidation. Alternatively, carbon
can be formed into fluid hydrocarbon for easy storage and later
combustion or reformation. Hydrocarbon formation requires a supply
of hydrogen molecules, atoms, or ions in a suitable form to combine
with carbon at the cathode, in some embodiments. Other product
collection involves, in some embodiments, the collection of oxygen
for storage and later use.
In still other embodiments, an electrolyzer cell is capable of
performing other electrolysis tasks, such as electroplating. In
such embodiments, at least one metal oxide functions as a solid
electrolyte shuttling at least one ion to complete an electrical
circuit.
[0112] In some embodiments, the electrodes of the electrolyzer cell
are adapted for the particular electrochemistry expected to occur
at the given electrode. For example, the electrode can comprise one
or more catalytic materials to facilitate the electrochemical
reaction. Catalytic materials can comprise transition metals
including, but not limited to, platinum, palladium, rhodium,
nickel, cerium, gold, silver, zinc, lead, ruthenium, rhenium, or
mixtures thereof. Catalytic materials, in some embodiments, are
disposed in one or a plurality of metal oxide layers coating the
electrode. In another example, the electrode can exhibit increased
surface area, for example, with porosity, electrode geometry, or a
combination thereof. Electrodes comprising catalytic materials can
optionally demonstrate compositional gradients based on the
distribution of the catalytic materials in a plurality of metal
compound layers proximal to the electrodes. In one embodiment, an
electrode comprises a substrate and a plurality of metal oxide
layers disposed on the substrate, wherein metal oxide layers
proximal to the substrate comprise greater amounts of catalytic
material than metal oxide layers distal to the substrate. Moreover,
in another embodiment, metal oxide layers distal to the substrate
comprise greater amounts of catalytic material than metal oxide
layers proximal to the substrate.
[0113] Solid oxide cells acting as electrolyzers operate at any
suitable temperature. In some embodiments, a solid oxide cell
comprising a first electrode, a second electrode, an electrolyte
interposed between the first electrode and the second electrode,
and optionally at least one electrode-electrolyte transition layer
has an operating temperature less than about 1000.degree. C. or
less than about 900.degree. C. In another embodiment, a solid oxide
cell of the present invention has an operating temperature of less
than about 800.degree. C., less than about 700.degree. C., less
than about 600.degree. C., or less than about 500.degree. C. In a
further embodiment, a solid oxide cell of the present invention has
an operating temperature of less than about 300.degree. C., less
than about 200.degree. C., less than about 100.degree. C., less
than about 50.degree. C., or less than about 25.degree. C.
III. Solid Oxide Cells Useful as Sensors
[0114] Some embodiments of the present invention provide solid
oxide sensors or components thereof. Like the fuel cells and
electrolyzer cells described above, sensors of the present
invention comprise at least one metal oxide. In some embodiments,
at least one ion passes through that metal oxide during cell
operation. In other embodiments, the solid oxide cells useful as
sensors or components thereof are substantially identical to the
solid oxide cells and components described above. The metal oxide
of sensors in certain embodiments has been made according to a
process comprising: [0115] applying at least one metal compound to
a substrate, and [0116] converting at least some of the at least
one metal compound to the at least one metal oxide.
[0117] Sensors according to various embodiments of the present
invention can be used to detect any suitable analyte or analytes.
Oxygen sensors, useful as lambda sensors in automotive exhaust
systems, or as oxygen partial pressure detectors in rebreather
systems, represent some applications for embodiments. Other
sensors, such as gas sensors including but not limited to CO,
CO.sub.2, H.sub.2, NO.sub.N, and SO.sub.N; ion sensors including
but not limited to pH meters, K.sup.+, and Na.sup.+; biosensors
including but not limited to glucose sensors and other enzyme
electrodes; electrochemical breathalyzers; and electronic noses;
represent other applications for embodiments of the present
invention. Many such sensors function at least in part due to the
diffusion of an ion through an electrolyte, which electrolyte
comprises at least one metal oxide. Accordingly, additional
embodiments provide a method for detecting at least one analyte,
comprising:
providing at least one sensor for the at least one analyte, wherein
the at least one sensor comprises at least one metal oxide made by
a process comprising:
[0118] applying at least one metal oxide to a substrate, and
[0119] converting at least some of the at least one metal compound
to the at least one metal oxide; and
passing at least one ion through the at least one metal oxide to
detect the at least one analyte. Passing an ion through a metal
oxide can include any suitable transport mechanism, such as, for
example, diffusion. In addition, movement along metal oxide crystal
grain boundaries represents another transport mechanism, in some
embodiments. Detecting an analyte can indicate obtaining any useful
information about the analyte, such as, for example, determining
its mere presence, concentration, partial pressure, oxidation
state, or combinations thereof. And, sensors of the present
invention can be designed for any suitable environment, such as
solid, semisolid (e.g., soil), liquid, gas, plasma, and
combinations thereof. Also, such sensors can be designed for any
suitable operating temperature, ranging from the very cold to the
very hot. Some solid oxide cells useful as sensors according to the
present invention have an operating temperature of below about
-195.degree. C., below about -182.degree. C., below about
-77.degree. C., from about -78.degree. C. to about 0.degree. C.,
from about 0.degree. C. to about 100.degree. C., from about
100.degree. C. to about 400.degree. C., from about 400.degree. C.
to about 600.degree. C., from about 600.degree. C. to about
900.degree. C., from about 900.degree. C. to about 1200.degree. C.,
or above about 1200.degree. C. Other embodiments useful as sensors
have operating temperatures below about 0.degree. C., above about
0.degree. C., above about 100.degree. C., or above about
500.degree. C.
[0120] A few embodiments of the present invention provide solid
oxide cells, useful as sensors, that enjoy one or more advantages
over conventional sensors. In some embodiments, the at least one
metal oxide has a certain thickness, thinner than conventional
sensors. In other embodiments, the solid oxide cell operates at a
lower temperature, compared to conventional sensors. Still other
embodiments provide smaller sensors. Even other embodiments provide
sensors made from less-expensive materials. Additional embodiments
have better-matched coefficients of thermal expansion between two
or more materials in the cell. Still other embodiments provide one
or more concentration gradients, one or more porosity gradients, or
combinations thereof.
[0121] Further embodiments of the present invention provide a
sensor comprising at least two electrodes separated by at least one
metal oxide that functions as a solid electrolyte. In some of those
embodiments, the voltage difference between the at least two
electrodes corresponds to the concentration of the analyte being
detected at one of the electrodes. A first electrode functions as a
reference electrode, and is exposed to a reference environment.
Suitable reference environments include, but are not limited to,
air, vacuum, standard solutions, and environments of known or
controlled composition. In some embodiments, the reference
environment is formed by arranging one or more materials that
substantially isolate the reference electrode from the environment
being measured. The second electrode is exposed to the environment
being measured. Optionally, the second electrode comprises one or
more catalytic materials. In some embodiments, at least one
catalytic material is chosen from platinum, palladium, rhodium,
nickel, cerium, gold, silver, zinc, lead, ruthenium, rhenium, and
combinations thereof. In operation, the first and second electrodes
are placed in electrical communication with one or more devices
that can measure, for example, the voltage difference, the current,
the resistance, or combinations thereof, between the two
electrodes. Such devices are known in the art. Optionally, heat or
cooling can be supplied to one or both electrodes, the electrolyte,
or combinations thereof. Heat or cooling can come from any suitable
source, such as, for example, one or more electrical resistance
heaters, chemical reaction, thermal fluid in thermal communication
with the sensor, the measured environment, and combinations
thereof.
[0122] In some embodiments, a reference voltage is supplied to the
electrodes, and the current needed to maintain the reference
voltage corresponds to the concentration of the analyte being
measured. For example, U.S. Pat. No. 7,235,171, describes
two-electrode hydrogen sensors comprising barium-cerium oxide
electrolyte. The '171 patent also indicates that various other
metal oxides also function as electrolytes in hydrogen sensors,
including selenium cerium oxides, selenium cerium yttrium oxides,
and calcium zirconium oxides, which conduct protons, and oxygen
anion conductors. The '171 patent is incorporated herein by
reference.
[0123] In other embodiments, a gas permeable porous platinum
measuring electrode is exposed to a measured environment that
contains a partial pressure of oxygen. At least one metal oxide,
such as, for example, yttria-stabilized zirconia, separates the
measuring electrode from a gas permeable porous platinum reference
electrode that is exposed to air. The voltage difference, current,
or both between the electrodes can be measured and correlated to
the difference of partial pressure of oxygen between the measured
environment and air. In some embodiments, the measured environment
is an exhaust stream from the combustion of hydrocarbons.
[0124] In still other embodiments, at least two pairs of electrodes
appear, wherein at least one metal oxide separates the electrodes
in each pair. One of the two pairs functions as a reference cell,
while the other of the two pairs functions as a measuring cell, in
some embodiments. Further embodiments provide, in a first pair of
electrodes, a reference electrode exposed to a reference
environment and a Nernst electrode exposed to the measured
environment. At least one metal oxide that functions as a solid
electrolyte is situated between the reference electrode and the
Nernst electrode. In a second pair of electrodes, an inner pump
electrode is separated from an outer pump electrode, with at least
one metal oxide functioning as a solid electrolyte situated between
the inner and outer pump electrodes. The inner pump electrode and
the Nernst electrode are exposed to the environment to be measured
optionally through a diffusion barrier. In operation, an external
reference voltage is applied across the pump electrodes. The
current needed to maintain the reference voltage across the pump
electrodes provides a measure of the analyte concentration in the
measured environment. For a conventional broadband lambda sensor
containing such a pair of electrodes, see U.S. Pat. No. 7,083,710
B2, which is incorporated herein by reference in its entirety.
Optionally, a sensor of the present invention is adapted to
electrically communicate with control circuitry that smoothes
operation of the sensor before the sensor has achieved standard
operating conditions, such as temperature. See, for example, U.S.
Pat. No. 7,177,099 B2, which is also incorporated herein by
reference.
[0125] Thus, certain embodiments of the present invention provide
so-called narrow band sensors such as lambda sensors that fluctuate
between lean and rich indications. Other embodiments provide
broadband sensors such as lambda sensors that indicate the partial
pressure of oxygen, and thereby the degree of leanness or richness
of an air-fuel mixture.
[0126] Some embodiments provide more than two electrodes. For
example, a sensor according to the present invention may contain a
plurality of measuring electrodes. For another example, a sensor
may comprise a plurality of reference electrodes. In another
example, a sensor may comprise, or be adapted to electrically
communicate with, a standard electrode or other device providing
information useful to the operation of the sensor.
[0127] In still other embodiments of the present invention, a
sensor is made by applying at least one metal compound to a
substrate, and converting at least some of the at least one metal
compound to at least one metal oxide. Metal compounds include those
described herein, such as, for example, metal carboxylates, metal
alkoxides, and metal .beta.-diketonates. Also, metal compounds
containing at least one metal atom and combinations of two or more
ligands can function as metal compounds.
[0128] In some embodiments, the at least one sensor or at least one
component thereof can be made in any suitable manner. For example,
the at least one metal oxide can be formed on any suitable
substrate. Such substrates include, but are not limited to, one or
more metals, plastics, ceramics, cermets, semiconductors,
insulators, metal oxides, and combinations thereof. In some
embodiments, the substrate is an electrode. At least one metal
oxide is formed on the substrate by applying at least one metal
compound to the substrate, and converting at least some of the at
least one metal compound to at least one metal oxide. In some
embodiments, the at least one metal compound is fully converted to
at least one metal oxide. Certain embodiments provide porous
substrates, while others provide non-porous substrates. Still other
embodiments provide fluid-permeable substrates, while others
provide substrates that are substantially impermeable to fluid.
[0129] In some embodiments, a plurality of metal oxide layers are
formed on the substrate. In one embodiment, for example, a method
of making a sensor or at least one component thereof comprises
forming a plurality of metal oxide layers on the substrate, wherein
each layer of metal oxide is formed on a preceding layer by
applying a metal carboxylate composition to the preceding layer,
the metal carboxylate composition comprising at least one metal
salt of a carboxylic acid. The metal carboxylate composition is
subsequently converted to at least one metal oxide, for example, by
exposing the metal carboxylate composition to heat. In still other
embodiments, the at least one metal compound comprises one or more
of catalytic materials, nanoparticles, substrate materials, and the
like. Yet other embodiments provide one or more concentration
gradients, porosity gradients, transition layers, or combinations
thereof.
[0130] Some embodiments of the present invention provide metal
oxides that are permeable to ions such as O.sup.2- ions. Other
embodiments provide metal oxides that may not necessarily be
permeable to ions. Still other embodiments provide metal oxides
that are permeable to ions, but such permeability is not required
for the function of the metal oxide in the embodiment. For example,
in certain embodiments, a metal oxide functions as a solid
electrolyte in a gas sensor, allowing diffusion of ions during
operation of the gas sensor. In other embodiments, a metal oxide
functions as a structural element of the gas sensor. In still other
embodiments, a metal oxide functions as both a solid electrolyte
and a structural element of the gas sensor. In still other
embodiments, one or more metal oxides are used alone or in
combination, for one or more functions in a gas sensor.
IV. Solid Oxide Cells Comprising Compositional Gradients and
Porosity Gradients
[0131] In order to reduce problems and disadvantages associated
with variances in coefficients of thermal expansion between
electrodes and electrolytes of solid oxide cells and to increase
ionic conductivities, electrolytes of some embodiments of the
present invention comprise compositional gradients. An electrolyte
of a solid oxide cell, in one embodiment, comprises a region
proximal to an electrode and a region distal to the electrode
wherein the region proximal to the electrode comprises a greater
amount of electrode material than the region distal to the
electrode. An electrode, for example, comprises
La.sub.1-xSr.sub.xMnO.sub.3 [lanthanum strontium doped manganite
(LSM)]. The region of the electrolyte proximal to the electrode
comprises greater amounts of LSM in comparison with the region of
the electrolyte distal from the electrode.
[0132] In another embodiment, an electrolyte of a solid oxide cell
comprises a plurality of metal oxide layers. Metal oxide layers of
the electrolyte proximal to the electrode comprise greater amounts
of electrode material than metal oxide layers of the electrolyte
distal to the electrode. An electrode, for example, comprises a
porous metal or metal carbide body (or substrate) onto which a thin
film surface treatment has been applied and that consists of a
material suitable for use as the air electrode (cathode) of a solid
oxide fuel cell (such as LSM). Metal oxide layers of an electrolyte
proximal to the electrode, in one embodiment, comprise greater
amounts of LSM in comparison with metal oxide layers of the
electrolyte distal from the electrode. Incorporating greater
amounts of electrode material in electrolyte layers proximal or
adjacent to the electrode in a solid oxide cell establishes a
compositional gradient among the electrolyte layers. Such a
compositional gradient can permit layers proximal to the electrode
to demonstrate a coefficient of thermal expansion that better
matches the coefficient of thermal expansion of the electrode. As a
result, disparities in coefficients of thermal expansion between
the electrode and the electrolyte can be reduced or eliminated
leading to a more stable solid oxide cell. Reducing the variances
in coefficients of thermal expansion between solid oxide cell
component layers can reduce or inhibit degradative pathways such as
electrode and/or electrolyte cracking as well as
electrode/electrolyte delamination. Reduction or inhibition of
these pathways results in a more stable and efficient cell.
[0133] In view of enhanced stabilities provided by a compositional
gradient, in some embodiments, a solid oxide cell comprises a first
electrode comprising a first material and an electrolyte comprising
a first region proximal to the first electrode and a second region
distal to the first electrode, wherein the first region of the
electrolyte comprises a greater amount of the first material than
the second region of the electrolyte.
[0134] In another embodiment, comprising a porous metal (or metal
carbide) body (or substrate) onto which a thin film surface
treatment has been applied and that comprises a first material, and
an electrolyte comprising a plurality of layers of an electrolyte
material, the layers of the electrolyte material proximal or
adjacent to the first electrode further comprise a greater amount
of the first material of the first electrode than layers of the
electrolyte distal or spaced apart from the first electrode. The
first material of the first electrode and the plurality of
electrolyte layers, according to some embodiments of the present
invention, can comprise any of the materials suitable for use as
electrodes and/or electrolytes. Moreover, the first electrode and
plurality of electrolyte layers can display any of the physical
parameters, such as thickness, porosity, and average grain size,
recited for electrodes and/or electrolytes hereinabove.
[0135] Additionally, in order to reduce problems and disadvantages
associated with variances in coefficients of thermal expansion
between electrode and electrolytes of solid oxide cells,
electrodes, in some embodiments of the present invention comprise
compositional gradients. An electrode, in one embodiment, comprises
a region proximal to the electrolyte and a region distal to the
electrolyte, wherein the region proximal to the electrolyte
comprises a greater amount of electrolyte material than the region
of the electrode distal to the electrolyte. In another embodiment,
an electrode of a solid oxide cell comprises a plurality of layers.
Layers of the electrode proximal to the electrolyte comprise a
greater amount of electrolyte material than layers of the electrode
distal to the electrolyte. A solid oxide cell, in some embodiments,
comprises a first electrode comprising a plurality of layers of a
first material and an electrolyte comprising an electrolyte
material disposed on the first electrode, wherein layers of the
first material proximal or adjacent to the electrolyte further
comprise a greater amount of the electrolyte material than layers
of the first material distal or spaced apart from the
electrolyte.
[0136] The first material of the plurality of electrode layers and
the electrolyte material, according to some embodiments of the
present invention, can comprise any of the materials suitable for
use as electrodes and/or electrolytes. Additionally, the
electrolyte and plurality of electrode layers can display any of
the physical parameters, such as thickness, porosity, and average
grain size, recited for electrodes and/or electrolytes
hereinabove.
[0137] In addition to variances in coefficients of thermal
expansion, solid oxide fuel cells of some embodiments of the
present invention also address fuel, air, reactant, and product
delivery and removal mechanisms by providing electrodes comprising
porosity gradients. Electrodes of solid oxide fuel cells are
optionally porous in order to allow the ingress of air and fuel to
the electrolyte and the egress of other gases produced or not
consumed by the fuel cell. Similarly, electrodes of cells other
than fuel cells may be porous, to allow for introduction of one or
more reactants, and removal of one or more products, from the
electrode. In one embodiment, a solid oxide cell comprises a solid
electrolyte disposed on a first electrode, the first electrode
comprising a first region proximal to the solid electrolyte and a
second region distal to the electrolyte, wherein the first region
has a porosity less than the second region. Alternatively, in
another embodiment, the first region of the electrode has a
porosity that is greater than the second region of the
electrode.
[0138] Moreover, in another embodiment, a solid oxide cell
comprises a first electrode comprising a plurality of layers of a
first material and an electrolyte disposed on the first electrode,
wherein layers of the first material proximal to the electrolyte
have porosities less than layers of the first material distal to
the electrolyte. In one embodiment, for example, layers of the
first material proximal to the electrolyte have a porosity ranging
from about 5 percent to about 10 percent while layers of the first
material distal to the electrolyte have a porosity ranging from
about 40 to about 70 percent. Alternatively, in another embodiment,
layers of the first material proximal to the solid electrolyte have
porosities greater than layers of the first material distal to the
solid electrolyte.
[0139] Establishing a porosity gradient among a plurality of layers
of an electrode permits the electrode to better match the porosity
of the electrolyte without producing a pore structure within the
electrode that is unduly restrictive to air, fuel, reactant, or
product flow. Porosity can be controlled by any suitable method,
such as, for example, by including particles such as nanoparticles
in the compositions used to manufacture an electrode or
electrolyte, pore-forming agents that release gas during
manufacture, substances that can be dissolved, melted, or sublimed
and thereby removed after a given layer has been manufactured, and
combinations thereof. In some embodiments, one or more organic
compounds such as corn starch can be included in the composition,
which organic compounds are burned away upon sintering in the
presence of oxygen to leave a porous structure upon cooling. A
porosity gradient is established by including an increasing or
decreasing amount of pore-forming agent in the compositions used to
form subsequent layers of electrode or electrolyte, for
example.
V. Electrodes of Solid Oxide Cells
[0140] In another aspect, the present invention provides electrodes
operable to be used in solid oxide cells as well as other
applications. Electrodes of the present invention, in some
embodiments, are resistant to harsh environments and various
chemical species which can foul the electrodes, such as sulfur and
carbon. In one embodiment, the present invention provides an
electrode comprising a substrate comprising a first material, a
coating comprising at least one layer of at least one metal oxide
disposed on the substrate, and a substrate-coating transition layer
interposed between the substrate and the coating. In some
embodiments, a coating comprises a plurality of layers of at least
one metal oxide disposed on the substrate. An electrode, in one
embodiment, is an anode. An electrode in another embodiment is a
cathode. In some embodiments, the metal oxide coating of an
electrode can protect the electrode substrate from corrosion and/or
degradation.
[0141] Turning now to components that can be used in electrodes of
the present invention, electrodes of the present invention, in some
embodiments, comprise a substrate. In some embodiments, a substrate
comprises silicon carbide doped with titanium. In other
embodiments, a substrate comprises La.sub.1-xSr.sub.xMnO.sub.3
[lanthanum strontium doped manganite (LSM)]. In another embodiment,
a substrate comprises porous steel alloys. In one embodiment, a
porous steel alloy comprises steel alloy 52. In some embodiments, a
porous steel alloy suitable for use as an electrode substrate
comprises steel alloy 316, stainless steel alloy 430, Crofer 22
APU.RTM. (Thyssen Krupp), E-Brite.RTM. (Alleghany Ludlum),
HASTELLOY.RTM. C-276, INCONEL.RTM. 600, or HASTELLOY.RTM. X, each
of which is commercially available from Mott Corporation of
Farmington, Conn. In a further embodiment, a substrate comprises
any metal or alloy known to one of skill in the art operable to
serve as an electrode. Some embodiments of the present invention
provide electrode substrates comprising at least one metal, at
least one metal carbide, or a combination thereof. In some of those
embodiments, the electrode substrate material may have electrical,
structural, and mechanical properties that are better than those of
ceramic electrodes.
[0142] Electrode substrates, according to further embodiments of
the present invention, are porous. In some embodiments, a substrate
has a porosity ranging from about 5% to about 40%. In another
embodiment, a substrate has a porosity ranging from about 10% to
about 30% or from about 15% to about 25%. In a further embodiment,
a substrate has a porosity greater than about 40%. A substrate, in
some embodiments, has a porosity ranging from about 40% to about
60%. In one embodiment, a substrate has a porosity greater than
about 60%.
[0143] In addition to a substrate, some electrodes of the present
invention optionally comprise a coating disposed on the substrate,
the coating comprising at least one layer of at least one metal
oxide. In some embodiments, a coating disposed on the substrate
comprises a plurality of layers comprising one or more metal
oxides. Metal oxide layers suitable for use in electrodes of the
present invention can comprise any of the metal oxides recited
herein, including cerium samarium oxides. Some embodiments of the
present invention provide at least one metal oxide coating disposed
on the electrode substrate that can act as an electrolyte, an
electrode-electrolyte transition layer, a concentration-gradient
layer, a matching layer for coefficients of thermal expansion, an
electrical insulator, or a combination thereof, among other
functions.
[0144] Substrate coatings comprising one or more metal oxide
layers, according to some embodiments of the present invention, are
porous. In one embodiment, a coating has a porosity ranging from
about 5% to about 40%. In another embodiment, a coating has a
porosity ranging from about 10% to about 30% or from about 15% to
about 25%. In a further embodiment, a substrate coating has a
porosity greater than about 40%. A substrate coating, in some
embodiments, has a porosity ranging from about 40% to about 60%. In
one embodiment, a substrate coating has a porosity greater than
about 60%.
[0145] Substrate coatings can have any desired thickness. In one
embodiment a substrate coating has a thickness ranging from about 1
nm to about 1 micron. In another embodiment, a substrate coating
has a thickness ranging from about 50 nm to about 750 .mu.m, from
about 500 nm to about 500 .mu.m, from about 1 .mu.m to about 350
.mu.m, or from about 10 .mu.m to about 200 .mu.m. In a further
embodiment, a substrate coating has a thickness ranging from about
50 .mu.m to about 100 .mu.m. In some embodiments wherein a coating
comprises a plurality of metal oxide layers, each metal oxide layer
has a thickness ranging from about 5 nm to about 15 nm, wherein the
total thickness of the coating is the summation of the thicknesses
of the individual layers.
[0146] In some embodiments of electrodes of the present invention,
a substrate-coating transition layer is interposed between the
substrate and the coating. A substrate-coating transition layer
comprises both substrate and coating materials. By comprising both
substrate and coating materials, the substrate-coating transition
layer, in some embodiments, is operable to reduce disparities in
coefficients of thermal expansion between the substrate and the
metal oxide coating of the electrode. Reducing such disparities can
have an inhibitory effect on degradative pathways such as cracking
or delamination between the substrate and metal oxide coating.
Moreover, a substrate-coating transition layer provides increased
stability by anchoring the metal oxide coating to the
electrode.
[0147] In some embodiments, a substrate-coating transition layer
has a thickness ranging from about 3 nm to about 100 nm or from
about 20 nm to about 80 nm. In another embodiment, a
substrate-coating transition layer has a thickness ranging from
about 30 nm to about 60 nm or from about 40 nm to about 50 nm. In a
further embodiment, a substrate-coating transition layer has a
thickness less than about 10 nm or greater than about 100 nm.
[0148] Electrodes, according to some embodiments of the present
invention, further comprise catalytic materials. Catalytic
materials can comprise transition metals including, but not limited
to, platinum, palladium, rhodium, nickel, cerium, gold, silver,
zinc, lead, ruthenium, rhenium, or mixtures thereof. Catalytic
materials, in some embodiments, are disposed in one or a plurality
of metal oxide layers coating the substrate of an electrode. The
combination of a metal oxide with pure metals or alloys, in some
embodiments, produces a cermet. Electrodes of solid oxide fuel
cells further comprising catalytic materials can function as fuel
reformers operable to convert hydrocarbon fuels into hydrogen for
subsequent use in the solid oxide fuel cell, in some embodiments.
Moreover, electrodes further comprising catalytic materials can
function as fuel reformers upstream and independent from the solid
oxide fuel cell in other embodiments.
[0149] Electrodes comprising catalytic materials can additionally
demonstrate compositional gradients based on the distribution of
the catalytic materials in the plurality of metal oxide layers. In
one embodiment, an electrode comprises a substrate and a plurality
of metal oxide layers disposed on the substrate, wherein metal
oxide layers proximal to the substrate comprise greater amounts of
catalytic material than metal oxide layers distal to the substrate.
Moreover, in another embodiment, metal oxide layers distal to the
substrate comprise greater amounts of catalytic material than metal
oxide layers proximal to the substrate. In one embodiment, for
example, metal oxide layers distal to the substrate comprise about
5 weight percent catalytic material while metal oxide layers
proximal to the substrate comprise about 1 weight percent catalytic
material.
VI. Interconnects of Solid Oxide Cells
[0150] In another aspect, the present invention provides
interconnects operable to be used in solid oxide cells as well as
other applications. Interconnects of the present invention, in some
embodiments, are resistant to harsh environments and chemical
species which can degrade the interconnects. In one embodiment, the
present invention provides an interconnect comprising a substrate
comprising a first material, a coating composition comprising at
least one layer of at least one metal oxide disposed on the
substrate, and a substrate-coating transition layer interposed
between the substrate and the coating. In some embodiments, a
coating composition comprises a plurality of metal oxide layers.
One or a plurality of metal oxide coatings can assist in protecting
a metallic or ceramic interconnect substrate from degradative
conditions and/or chemical species.
[0151] Turning now to components that can be used in various
applications of the present invention, interconnects, in some
embodiments, comprise substrates. In some embodiments, substrates
comprise metal oxides including, but not limited to, lanthanum and
yttrium chromites. In other embodiments, a substrate comprises
metals or alloys, such as chromium based alloys. In one embodiment,
a chromium based alloy comprises 5 weight percent iron and 1 weight
percent yttria. In another embodiment, a substrate comprises at
least one ferritic steel. In a further embodiment, a substrate
comprises any metal operable to sufficiently transfer charge
carriers into or from an external circuit. Thus, in some
embodiments, interconnects of the present invention are adaptable
to provide electrical communication between at least one electrode
and an external circuit. In further embodiments, interconnects are
adaptable to provide material communication between at least one
electrode and an external source of at least one material, and/or
at least one exit for at least one material. For example, an
interconnect can provide air or oxygen to the cathode of a solid
oxide fuel cell. For another example, an interconnect can provide
an exhaust conduit for water or steam to exit a solid oxide fuel
cell. For yet another example, an interconnect can provide a
conduit to a storage system for hydrogen generated at the cathode
of a solid oxide electrolyzer cell. In still other embodiments, an
interconnect provides both electrical and material communication
between at least one electrode and an external circuit and external
sources and/or reservoirs and/or exhaust for material. Optionally,
an interconnect may be adapted to provide thermal communication
between an electrode and an external source or sink for thermal
energy.
[0152] Accordingly, interconnects can have any desired shape.
Wires, films, monoliths, porous monoliths, disks, tubes, pipes,
among other shapes, are possible. Connections between an
interconnect and an electrode can adopt any suitable form. In some
embodiments, the same piece of metal (or metal carbide, cermet, or
other material) forms the substrate for the electrode and for the
interconnect; in such embodiments, the portion of the metal that
engages in the electrochemical reaction in the cell is the
electrode portion, while the portion of the metal providing
communication outside the cell is the interconnect portion. In
other embodiments, electrical contact between the interconnect and
the electrode are made with any suitable connection, such as, for
example, welding, stamping, melt fusion, mechanical connections
such as bolts or rivets, conductive paints such as silver paint,
sputtered metals, and conductive adhesives, as well as combinations
thereof. Such connections can be made before, during, or after
formation of metal oxides as described herein.
[0153] Interconnect substrates can have any desired thickness. In
one embodiment a substrate has a thickness ranging from about 1 nm
to about 1 mm. In another embodiment, a substrate has a thickness
ranging from about 50 nm to about 750 .mu.m, from about 500 nm to
about 500 .mu.m, from about 1 .mu.m to about 350 .mu.m, or from
about 10 .mu.m to about 200 .mu.m. In a further embodiment, a
substrate has a thickness ranging from about 50 .mu.m to about 100
.mu.m.
[0154] In addition to a substrate, an interconnect of some
embodiments of the present invention comprises a coating disposed
on the substrate, the coating comprising at least one layer of at
least one metal oxide. In some embodiments, a coating disposed on
the substrate comprises a plurality of layers comprising one or
more metal oxides. Metal oxide layers suitable for use in
interconnects of the present invention can comprise any of the
metal oxides recited herein, such as, for example, any of the
cerium samarium oxides.
[0155] Substrate coatings comprising one or more metal oxide
layers, according to some embodiments of the present invention, are
porous. In one embodiment, a coating has a porosity ranging from
about 5% to about 40%. In another embodiment, a coating has a
porosity ranging from about 10% to about 30% or from about 15% to
about 25%. In a further embodiment, a substrate coating has a
porosity greater than about 40%. A substrate coating, in some
embodiments, has a porosity ranging from about 40% to about 60%. In
one embodiment, a substrate coating has a porosity greater than
about 60%.
[0156] Substrate coatings can have any desired thickness. In one
embodiment, a substrate coating has a thickness ranging from about
1 nm to about 1 micron. In another embodiment, a substrate coating
has a thickness ranging from about 50 nm to about 750 .mu.m, from
about 500 nm to about 500 .mu.m, from about 1 .mu.m to about 350
.mu.m, or from about 10 .mu.m to about 200 .mu.m. In a further
embodiment, a substrate coating has a thickness ranging from about
50 .mu.m to about 100 .mu.m. In some embodiments wherein a coating
comprises a plurality of metal oxide layers, each metal oxide layer
has a thickness ranging from about 5 nm to about 15 nm, wherein the
total thickness of the coating is the summation of the thicknesses
of the individual layers.
[0157] In some embodiments of interconnects of the present
invention, a substrate-coating transition layer is interposed
between the substrate and the coating. A substrate-coating
transition layer comprises both substrate and coating materials. By
comprising both substrate and coating materials, the
substrate-coating transition layer, in some embodiments, is
operable to reduce disparities in coefficients of thermal expansion
between the substrate and the metal oxide coating of the
interconnect. Reducing such disparities can have an inhibitory
effect on degradative pathways such as cracking or delamination
between the substrate and metal oxide coating. Moreover, a
substrate-coating transition layer provides increased stability by
anchoring the metal oxide coating to the electrode.
[0158] In some embodiments, a substrate-coating transition layer of
an interconnect has a thickness ranging from about 3 nm to about
100 nm or from about 20 nm to about 80 nm. In another embodiment, a
substrate-coating transition layer has a thickness ranging from
about 30 nm to about 60 nm or from about 40 nm to about 50 nm. In a
further embodiment, a substrate-coating transition layer has a
thickness less than about 10 nm or greater than about 100 nm.
[0159] Additionally, in order to reduce problems and disadvantages
associated with variances in coefficients of thermal expansion
between interconnects and electrodes of solid oxide cells,
interconnects, in some embodiments of the present invention,
comprise compositional gradients. An interconnect, in one
embodiment, comprises a region proximal to a cathode and a region
distal to the cathode, wherein the region proximal to the cathode
has a greater amount of cathode material than the region of the
interconnect distal from the cathode. Moreover, in another
embodiment, an interconnect comprises a region proximal to an anode
and a region distal to the anode, wherein the region proximal to
the anode has a greater amount of anode material than the region of
the interconnect distal from the anode.
[0160] In another embodiment, an interconnect comprises a substrate
coated with a plurality of metal oxide layers. Layers of the
interconnect proximal to the cathode comprise greater amounts of
cathode material than layers of the interconnect distal from the
cathode. Moreover, in another embodiment, layers of the
interconnect proximal to the anode comprise greater amounts of
anode material than layers of the interconnect distal from the
anode.
VII. Methods of Making Solid Oxide Cells
[0161] In another aspect, the present invention provides methods of
making solid oxide cells. In one embodiment, a method of making a
solid oxide cell comprises providing a first electrode, applying a
metal compound composition to the first electrode, and converting
at least some of the metal compound composition to a metal oxide
composition. In some embodiments, the metal compound composition is
fully converted to a metal oxide composition. A metal compound
composition comprises at least one metal-containing compound that
can be at least partially converted to at least one metal oxide. In
some embodiments, the metal compound composition comprises at least
one metal carboxylate, at least one metal alkoxide, at least one
metal .beta.-diketonate, or a combination thereof.
[0162] A metal carboxylate comprises the metal salt of a carboxylic
acid, e.g., at least one metal atom and at least one carboxylate
moiety. In some embodiments of the methods of the present
invention, a metal salt of a carboxylic acid comprises a transition
metal salt. In other embodiments, a metal salt of a carboxylic acid
comprises a rare earth metal salt. In a further embodiment, metal
carboxylate compositions comprise a plurality of metal salts of
carboxylic acids. In one embodiment, a plurality of metal salts
comprises at least one rare earth metal salt of a carboxylic acid
and at least one transition metal salt of a carboxylic acid.
[0163] Metal carboxylates can be produced by a variety of methods
known to one skilled in the art. Non-limiting examples of methods
for producing the metal carboxylate are shown in the following
reaction schemes:
nRCOOH+Me.fwdarw.(RCOO).sub.nMe.sup.n++0.5nH.sub.2 (for alkaline
earth metals, alkali metals, and thallium)
nRCOOH+Me.sup.n+(OH).sub.n.fwdarw.(RCOO).sub.nMe.sup.n++nH.sub.2O
(for practically all metals having a solid hydroxide)
nRCOOH+Me.sup.n+(CO.sub.3).sub.0.5n.fwdarw.(RCOO).sub.nMe.sup.n++0.5nH.s-
ub.2O+0.5nCO.sub.2 (for alkaline earth metals, alkali metals and
thallium)
nRCOOH+Me.sup.n+(X).sub.n/m.fwdarw.(RCOO).sub.nMe.sup.n++n/mH.sub.mX
(liquid extraction, usable for practically all metals having solid
salts)
[0164] In the foregoing reaction schemes, X is an anion having a
negative charge m, such as, e.g., halide anion, sulfate anion,
carbonate anion, phosphate anion, among others; n is a positive
integer; and Me represents a metal atom. R in the foregoing
reaction schemes can be chosen from a wide variety of radicals.
Suitable carboxylic acids for use in making metal carboxylates
include, for example:
[0165] Monocarboxylic acids: Monocarboxylic acids where R is
hydrogen or unbranched hydrocarbon radical, such as, for example,
HCOOH--formic, CH.sub.3COOH--acetic,
CH.sub.3CH.sub.2COOH--propionic, CH.sub.3CH.sub.2CH.sub.2COOH
(C.sub.4H.sub.8O.sub.2)--butyric, C.sub.5H.sub.10O.sub.2--valeric,
C.sub.6H.sub.12O.sub.2--caproic, C.sub.7H.sub.14--enanthic;
further: caprylic, pelargonic, undecanoic, dodecanoic, tridecylic,
myristic, pentadecylic, palmitic, margaric, stearic, and
nonadecylic acids; Monocarboxylic acids where R is a branched
hydrocarbon radical, such as, for example,
(CH.sub.3).sub.2CHCOOH--isobutyric,
(CH.sub.3).sub.2CHCH.sub.2COOH--3-methylbutanoic,
(CH.sub.3).sub.3CCOOH--trimethylacetic, including VERSATIC 10
(trade name) which is a mixture of synthetic, saturated carboxylic
acid isomers, derived from a highly-branched C.sub.10
structure;
[0166] Monocarboxylic acids in which R is a branched or unbranched
hydrocarbon radical containing one or more double bonds, such as,
for example, CH.sub.2.dbd.CHCOOH--acrylic,
CH.sub.3CH.dbd.CHCOOH--crotonic,
CH.sub.3(CH.sub.2).sub.7CH.dbd.CH(CH.sub.2).sub.7COOH--oleic,
CH.sub.3CH.dbd.CHCH.dbd.CHCOOH--hexa-2,4-dienoic,
(CH.sub.3).sub.2C.dbd.CHCH.sub.2CH.sub.2C(CH.sub.3).dbd.CHCOOH--3,7-dimet-
hylocta-2,6-dienoic,
CH.sub.3(CH.sub.2).sub.4CH.dbd.CHCH.sub.2CH.dbd.CH(CH.sub.2).sub.7COOH--l-
inoleic, further: angelic, tiglic, and elaidic acids;
[0167] Monocarboxylic acids in which R is a branched or unbranched
hydrocarbon radical containing one or more triple bonds, such as,
for example, CH.ident.CCOOH--propiolic, CH.sub.3CCCOOH--tetrolic,
CH.sub.3(CH.sub.2).sub.4CCCOOH--oct-2-ynoic, and stearolic acids;
Monocarboxylic acids in which R is a branched or unbranched
hydrocarbon radical containing one or more double bonds and one or
more triple bonds;
[0168] Monocarboxylic acids in which R is a branched or unbranched
hydrocarbon radical containing one or more double bonds and one or
more triple bonds and one or more aryl groups;
[0169] Monohydroxymonocarboxylic acids in which R is a branched or
unbranched hydrocarbon radical that contains one hydroxyl
substituent, such as, for example, HOCH.sub.2COOH--glycolic,
CH.sub.3CHOHCOOH--lactic, C.sub.6H.sub.5CHOHCOOH--amygdalic, and
2-hydroxybutyric acids;
[0170] Dihydroxymonocarboxylic acids in which R is a branched or
unbranched hydrocarbon radical that contains two hydroxyl
substituents, such as, for example,
(HO).sub.2CHCOOH--2,2-dihydroxyacetic acid;
[0171] Dioxycarboxylic acids, in which R is a branched or
unbranched hydrocarbon radical that contains two oxygen atoms each
bonded to two adjacent carbon atoms, such as, for example,
C.sub.6H.sub.3(OH).sub.2COOH--dihydroxy benzoic,
C.sub.6H.sub.2(CH.sub.3)(OH).sub.2COOH--orsellinic; further:
caffeic, and piperic acids;
[0172] Aldehyde-carboxylic acids in which R is a branched or
unbranched hydrocarbon radical that contains one aldehyde group,
such as, for example, CHOCOOH--glyoxalic acid;
[0173] Keto-carboxylic acids in which R is a branched or unbranched
hydrocarbon radical that contains one ketone group, such as, for
example, CH.sub.3COCOOH--pyruvic,
CH.sub.3COCH.sub.2COOH--acetoacetic, and
CH.sub.3COCH.sub.2CH.sub.2COOH--levulinic acids;
[0174] Monoaromatic carboxylic acids, in which R is a branched or
unbranched hydrocarbon radical that contains one aryl substituent,
such as, for example, C.sub.6H.sub.5COOH--benzoic,
C.sub.6H.sub.5CH.sub.2COOH--phenylacetic,
C.sub.6H.sub.5CH(CH.sub.3)COOH--2-phenylpropanoic,
C.sub.6H.sub.5CH.dbd.CHCOOH--3-phenylacrylic, and
C.sub.6H.sub.5CCCOOH--3-phenyl-propiolic acids;
Multicarboxylic Acids:
[0175] Saturated dicarboxylic acids, in which R is a branched or
unbranched saturated hydrocarbon radical that contains one
carboxylic acid group, such as, for example, HOOC--COOH--oxalic,
HOOC--CH.sub.2--COOH--malonic,
HOOC--(CH.sub.2).sub.2--COOH--succinic,
HOOC--(CH.sub.2).sub.3--COOH--glutaric,
HOOC--(CH.sub.2).sub.4--COOH--adipic; further: pimelic, suberic,
azelaic, and sebacic acids;
[0176] Unsaturated dicarboxylic acids, in which R is a branched or
unbranched hydrocarbon radical that contains one carboxylic acid
group and at least one carbon-carbon multiple bond, such as, for
example, HOOC--CH.dbd.CH--COOH--fumaric; further: maleic,
citraconic, mesaconic, and itaconic acids;
[0177] Polybasic aromatic carboxylic acids, in which R is a
branched or unbranched hydrocarbon radical that contains at least
one aryl group and at least one carboxylic acid group, such as, for
example, C.sub.6H.sub.4(COOH).sub.2--phthalic (isophthalic,
terephthalic), and
C.sub.6H.sub.3(COOH).sub.3--benzyl-tri-carboxylic acids;
[0178] Polybasic saturated carboxylic acids, in which R is a
branched or unbranched hydrocarbon radical that contains at least
one carboxylic acid group, such as, for example, ethylene diamine
N,N'-diacetic acid, and ethylene diamine tetraacetic acid (EDTA);
Polybasic oxyacids:
[0179] Polybasic oxyacids, in which R is a branched or unbranched
hydrocarbon radical containing at least one hydroxyl substituent
and at least one carboxylic acid group, such as, for example,
HOOC--CHOH--COOH--tartronic, HOOC--CHOH--CH.sub.2--COOH--malic,
HOOC--C(OH).dbd.CH--COOH--oxaloacetic,
HOOC--CHOH--CHOH--COOH--tartaric, and HOOC--CH.sub.2--C(OH)
COOH--CH.sub.2COOH--citric acids.
[0180] A metal compound composition, in some embodiments of the
present invention, comprises a solution of carboxylic acid salts of
one or more metals ("metal carboxylate"). A liquid metal
carboxylate composition can comprise a single metal, to form a
single metal carboxylate, or a mixture of metals, to form a
corresponding mixture of metal carboxylates. In addition, a liquid
metal carboxylate composition can contain different carboxylate
moieties. In some embodiments, a liquid metal carboxylate
composition contains a mixture of metals, as these compositions
form mixed oxides having various properties.
[0181] Solvent used in the production of liquid metal carboxylate
compositions, in some embodiments, comprise an excess of the liquid
carboxylic acid which was used to form the metal carboxylate salt.
In other embodiments, a solvent comprises another carboxylic acid,
or a solution of a carboxylic acid in another solvent, including,
but not limited to, organic solvents such as benzene, toluene,
xylene, chloroform, dichloromethane, or combinations thereof.
[0182] Carboxylic acids suitable for use generating liquid metal
carboxylate compositions, in some embodiments, are those which: (1)
can form a metal carboxylate, where the metal carboxylate is
soluble in excess acid or another solvent; and (2) can be vaporized
in a temperature range that overlaps with the oxide conversion
temperature range.
[0183] In some embodiments, a carboxylic acid has a formula
R--COOH, where R is alkyl, alkenyl, alkynyl or aryl.
[0184] In some embodiments, the monocarboxylic acid comprises one
or more carboxylic acids having the formula I below:
R.sup.o--C(R'')(R')--COOH (I)
wherein: R.sup.o is selected from H or C.sub.1 to C.sub.24 alkyl
groups; and R' and R'' are each independently selected from H and
C.sub.1 to C.sub.24 alkyl groups; wherein the alkyl groups of
R.sup.o, R', and R'' are optionally and independently substituted
with one or more substituents, which are alike or different, chosen
from hydroxy, alkoxy, amino, and aryl radicals, and halogen
atoms.
[0185] The term alkyl, as used herein, refers to a saturated
straight, branched, or cyclic hydrocarbon, or a combination
thereof, including C.sub.1 to C.sub.24, methyl, ethyl, n-propyl,
isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, cyclopentyl,
isopentyl, neopentyl, n-hexyl, isohexyl, cyclohexyl,
3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, heptyl,
octyl, nonyl, and decyl.
[0186] The term alkoxy, as used herein, refers to a saturated
straight, branched, or cyclic hydrocarbon, or a combination
thereof, including C.sub.1 to C.sub.24, methyl, ethyl, n-propyl,
isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, cyclopentyl,
isopentyl, neopentyl, n-hexyl, isohexyl, cyclohexyl,
3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, heptyl,
octyl, nonyl, and decyl, in which the hydrocarbon contains a
single-bonded oxygen atom that can bond to or is bonded to another
atom or molecule.
[0187] The terms alkenyl and alkynyl, as used herein, refer to a
straight, branched, or cyclic hydrocarbon, including C.sub.1 to
C.sub.24, with at least one double or triple bond,
respectively.
[0188] Alkyl, alkenyl, alkoxy, and alkynyl radicals are
unsubstituted or substituted with one or more alike or different
substituents independently chosen from halogen atoms, hydroxy,
alkoxy, amino, aryl, and heteroaryl radicals.
[0189] Moreover, the term aryl or aromatic, as used herein, refers
to a monocyclic or bicyclic hydrocarbon ring molecule having
conjugated double bonds about the ring. In some embodiments, the
ring molecule has 5- to 12-members, but is not limited thereto. The
ring may be unsubstituted or substituted having one or more alike
or different independently-chosen substituents, wherein the
substituents are chosen from alkyl, alkenyl, alkynyl, alkoxy,
hydroxyl, and amino radicals, and halogen atoms. Aryl includes, for
example, unsubstituted or substituted phenyl and unsubstituted or
substituted naphthyl.
[0190] The term heteroaryl as used herein refers to a monocyclic or
bicyclic aromatic hydrocarbon ring molecule having at least one
heteroatom chosen from O, N, P, and S as a member of the ring, and
the ring is unsubstituted or substituted with one or more alike or
different substituents independently chosen from alkyl, alkenyl,
alkynyl, hydroxyl, alkoxy, amino, alkylamino, dialkylamino, thiol,
alkylthio, .dbd.O, .dbd.NH, .dbd.PH, .dbd.S, and halogen atoms. In
some embodiments, the ring molecule has 5- to 12-members, but is
not limited thereto.
[0191] The alpha branched carboxylic acids, in some embodiments,
have an average molecular weight ranging from about 130 to 420
g/mol or from about 220 to 270 g/mol. The carboxylic acid may also
be a mixture of tertiary and quaternary carboxylic acids of Formula
I. VIK acids can be used as well. See U.S. Pat. No. 5,952,769, at
col. 6, 11. 12-51, which patent is incorporated herein by reference
in its entirety.
[0192] Either a single carboxylic acid or a mixture of carboxylic
acids can be used to form the liquid metal carboxylate. In some
embodiments, a mixture of carboxylic acids contains 2-ethylhexanoic
acid wherein R.sup.o is H, R'' is C.sub.2H.sub.5 and R' is
C.sub.4H.sub.9, in the formula (I) above. The use of a mixture of
carboxylates can provide several advantages. In one aspect, the
mixture has a broader evaporation temperature range, making it more
likely that the evaporation temperature of the acid mixture will
overlap the metal carboxylate decomposition temperature, allowing
the formation of a metal oxide coating. Moreover, the possibility
of using a mixture of carboxylates avoids the need and expense of
purifying an individual carboxylic acid.
[0193] Other metal compounds can be used to form metal oxides in
accordance with the present invention. Such metal compounds can be
used alone or in combination, or in combination with one or more
metal carboxylates. Metal compounds other than carboxylates and
those mentioned elsewhere include metal alkoxides and metal
.beta.-diketonates.
[0194] Metal alkoxides suitable for use in the present invention
include at least one metal atom and at least one alkoxide radical
--OR.sup.2 bonded to the at least one metal atom. Such metal
alkoxides include those of formula II:
M(OR.sup.2).sub.z (II)
[0195] in which M is a metal atom of valence z+;
[0196] z is a positive integer, such as, for example, 1, 2, 3, 4,
5, 6, 7, and 8;
[0197] R.sup.2 can be alike or different and are independently
chosen from unsubstituted and substituted alkyl, unsubstituted and
substituted alkenyl, unsubstituted and substituted alkynyl,
unsubstituted and substituted heteroaryl, and unsubstituted and
substituted aryl radicals,
[0198] wherein substituted alkyl, alkenyl, alkynyl, heteroaryl, and
aryl radicals are substituted with one or more alike or different
substituents independently chosen from halogen, hydroxy, alkoxy,
amino, heteroaryl, and aryl radicals.
[0199] In some embodiments, z is chosen from 2, 3, and 4.
[0200] Metal alkoxides are available from Alfa-Aesar and Gelest,
Inc., of Morrisville, Pa. Lanthanoid alkoxides such as those of Ce,
Nd, Eu, Dy, and Er are sold by Kojundo Chemical Co., Saitama,
Japan, as well as alkoxides of Al, Zr, and Hf, among others. See,
e.g.,
http://www.kojundo.co.jp/English/Guide/material/lanthagen.html.
[0201] Examples of metal alkoxides useful in embodiments of the
present invention include methoxides, ethoxides, propoxides,
isopropoxides, and butoxides and isomers thereof. The alkoxide
substituents on a give metal atom are the same or different. Thus,
for example, metal dimethoxide diethoxide, metal methoxide
diisopropoxide t-butoxide, and similar metal alkoxides can be used.
Suitable alkoxide substituents also may be chosen from:
[0202] 1. Aliphatic series alcohols from methyl to dodecyl
including branched and isostructured.
[0203] 2. Aromatic series alcohols: benzyl
alcohol--C.sub.6H.sub.5CH.sub.2OH; phenyl-ethyl alcohol
C.sub.8H.sub.10O; phenyl-propyl alcohol--C.sub.9H.sub.12O, and so
on.
[0204] Metal alkoxides useful in the present invention can be made
according to many suitable methods. One method includes converting
the metal halide to the metal alkoxide in the presence of the
alcohol and its corresponding base. For example:
MX.sub.z+zHOR.sup.2.fwdarw.M(OR.sup.2)z+zHX
[0205] in which M, R.sup.2, and z are as defined above for formula
II, and X is a halide anion.
[0206] Metal .beta.-diketonates suitable for use in the present
invention contain at least one metal atom and at least one
.beta.-diketone of formula III as a ligand:
##STR00001##
[0207] in which
[0208] R.sup.3, R.sup.4, R.sup.5, and R.sup.6 are alike or
different, and are independently chosen from hydrogen,
unsubstituted and substituted alkyl, unsubstituted and substituted
alkoxy, unsubstituted and substituted alkenyl, unsubstituted and
substituted alkynyl, unsubstituted and substituted heteroaryl,
unsubstituted and substituted aryl, carboxylic acid groups, ester
groups having unsubstituted and substituted alkyl, and combinations
thereof,
[0209] wherein substituted alkyl, alkoxy, alkenyl, alkynyl,
heteroaryl, and aryl radicals are substituted with one or more
alike or different substituents independently chosen from halogen
atoms, hydroxy, alkoxy, amino, heteroaryl, and aryl radicals.
[0210] It is understood that the .beta.-diketone of formula III may
assume different isomeric and electronic configurations before and
while chelated to the metal atom. For example, the free
.beta.-diketone may exhibit enolate isomerism. Also, the
.beta.-diketone may not retain strict carbon-oxygen double bonds
when the molecule is bound to the metal atom.
[0211] Examples of .beta.-diketones useful in embodiments of the
present invention include acetylacetone, trifluoroacetylacetone,
hexafluoroacetylacetone, 2,2,6,6-tetramethyl-3,5-heptanedione,
6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione, ethyl
acetoacetate, 2-methoxyethyl acetoacetate, benzoyltrifluoroacetone,
pivaloyltrifluoroacetone, benzoyl-pyruvic acid, and
methyl-2,4-dioxo-4-phenylbutanoate.
[0212] Other ligands are possible on the metal .beta.-diketonates
useful in the present invention, such as, for example, alkoxides
such as --OR.sup.2 as defined above, and dienyl radicals such as,
for example, 1,5-cyclooctadiene and norbornadiene.
[0213] Metal .beta.-diketonates useful in the present invention can
be made according to any suitable method. .beta.-diketones are well
known as chelating agents for metals, facilitating synthesis of the
diketonate from readily available metal salts.
Metal .beta.-diketonates are available from Alfa-Aesar and Gelest,
Inc. Also, Strem Chemicals, Inc. of Newburyport, Mass., sells a
wide variety of metal .beta.-diketonates on the internet at
http://www.strem.com/code/template.ghc?direct=cvdindex.
[0214] In some embodiments, a metal compound composition contains
one metal compound as its major component and one or more
additional metal compounds which may function as stabilizing
additives. Stabilizing additives, in some embodiments, comprise
trivalent metal compounds. Trivalent metal compounds include, but
are not limited to, chromium, iron, manganese and nickel
carboxylates. A metal compound composition, in some embodiments,
comprises both cerium and chromium carboxylates.
[0215] Metals suitable for use in forming metal compounds
including, but not limited to liquid metal carboxylates, metal
alkoxides, and metal .beta.-diketonates comprise lithium,
beryllium, sodium, magnesium, aluminum, silicon, potassium,
calcium, scandium, titanium, vanadium, chromium, manganese, iron,
cobalt, nickel, copper, zinc, gallium, germanium, arsenic, bromine,
rubidium, strontium, yttrium, zirconium, niobium, molybdenum,
technetium, ruthenium, rhodium, palladium, antimony, tellurium,
silver, cadmium, indium, tin, cesium, barium, lanthanum, cerium,
praseodymium, neodymium, promethium, samarium, europium,
gadolinium, terbium, dysprosium, holmium, erbium, thulium,
ytterbium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium,
irridium, gold, mercury, thallium, lead, bismuth, radium, actinium,
platinum, thorium, protactinium, uranium, neptunium, plutonium,
americium, berkelium, californium, einsteinium, fermium,
mendelevium, nobelium, lawrencium, or curium. Any of the foregoing
metals or combinations thereof can be used to form metal oxides
according to embodiments of the present invention.
[0216] In some embodiments, the amount of metal forming the major
component of the metal compound composition ranges from about 65
weight percent to about 97 weight percent or from about 80 weight
percent to about 87 weight percent of the total metal in the
compound composition. In other embodiments, the amount of metal
forming the major component of the metal compound composition
ranges from about 90 weight percent to about 97 weight percent of
the total metal present in the compound composition. In a further
embodiment, the amount of metal forming the major component of the
metal compound composition is less than about 65 weight percent or
greater than about 97 weight percent of the total metal present in
the compound composition.
[0217] In some embodiments, metal compounds operable to function as
stabilizing additives are present in amounts such that the total
amount of the metal in metal compounds which are the stabilizing
additives is at least 3% by weight of the total metal in the liquid
metal compound composition.
[0218] The amount of metal in a liquid metal compound composition,
according to some embodiments, ranges from about 20 to about 150
grams of metal per kilogram of liquid metal compound composition.
In other embodiments, the amount of metal in a liquid metal
compound composition ranges from about 30 to about 50 grams of
metal per kilogram of liquid metal compound composition. In a
further embodiment, a liquid metal compound composition comprises
from about 30 to about 40 grams of metal per kg of composition. In
one embodiment, a metal amount is less than about 20 grams of metal
per kilogram of liquid metal compound or greater than 150 grams of
metal per kilogram of liquid metal compound.
[0219] Liquid metal compound compositions, in some embodiments of
solid oxide cell production methods, further comprise one or more
catalytic materials. Catalytic materials, in such embodiments,
comprise transition metals including, but not limited to, platinum,
palladium, rhodium, nickel, cerium, gold, silver, zinc, lead,
ruthenium, rhenium, or mixtures thereof. Catalytic materials, in
some embodiments, are present in liquid metal compound compositions
in an amount ranging from about 0.5 weight percent to about 10
weight percent of the composition.
[0220] In other embodiments, liquid metal compound composition
further comprises nanoparticles operable to alter the pore
structure and porosity of the metal oxide resulting from the
conversion of the liquid metal compound composition. Nanoparticles,
in some embodiments, comprise metal oxide nanoparticles.
Nanoparticles, in some embodiments, are present in liquid metal
compound compositions in an amount ranging from about 0.5 percent
by volume to about 30 percent by volume of the liquid metal
compound composition. In another embodiment, nanoparticles are
present in the liquid metal compound composition in an amount
ranging from about 5 percent by volume to about 15 percent by
volume of the liquid metal compound composition.
[0221] In addition to liquids, metal compound compositions, in some
embodiments of methods of the present invention, comprise solid
metal compound compositions, vapor metal compound compositions, or
combinations thereof. In one embodiment, a solid metal compound
composition comprises one or more metal compound powders. In
another embodiment, a vapor metal compound composition comprises at
least one gas phase metal compound operable to condense on a
substrate prior to conversion to at least one metal oxide. In some
embodiments, the substrate is cooled to enhance condensation of the
vapor phase metal compound composition. In one embodiment, for
example, a substrate such as a steel coupon is placed in a vacuum
chamber, and the chamber is evacuated. Vapor of one or more metal
compounds, such as cerium (IV) 2-hexanoate, enters the vacuum
chamber and deposits on the steel substrate. Subsequent to
deposition, the metal compound is exposed to conditions operable to
convert the metal compound to a metal oxide. In a further
embodiment, a metal compound composition comprises gels chosen from
suitable gels including, but not limited to, sol-gels, hydrogels,
and combinations thereof.
[0222] Applying a metal compound composition to the first electrode
of a solid oxide cell can be accomplished by any suitable method,
such as those known to one of skill in the art. In one embodiment,
the first electrode is dipped into the liquid metal compound
composition. In another embodiment, a swab, sponge, dropper,
pipette, spray, brush or other applicator is used to apply the
liquid metal compound composition to the first electrode. In some
embodiments, a vapor phase metal compound composition is condensed
on the first electrode. In other embodiments, lithographic methods
can be used to apply the metal compound composition to the first
electrode.
[0223] A metal compound composition, in some embodiments, is
applied to the first electrode at a temperature less than about
250.degree. C. In other embodiments, a metal compound composition
is applied to the first electrode at a temperature less than about
200.degree. C., less than about 150.degree. C., less than about
100.degree. C., or less than about 50.degree. C. In a further
embodiment, a metal compound composition is applied to the first
electrode at room temperature.
[0224] An electrode, in some embodiments, is pretreated prior to
application of the metal compound composition. In one embodiment,
for example, the first electrode can be etched according to known
methods, for example, with an acid wash comprising nitric acid,
sulphuric acid, hydrochloric acid, phosphoric acid, or a
combination thereof, or with a base wash comprising sodium
hydroxide or potassium hydroxide, for example. In another
embodiment, the first electrode is polished, with or without the
aid of one or more chemical etching agents, abrasives, and
polishing agents, to make the surface either rougher or smoother.
In a further embodiment, the first electrode is pretreated such as
by carburizing, nitriding, plating, or anodizing.
[0225] Following application, the metal compound composition is at
least partially converted to a metal oxide. In some embodiments,
the metal compound composition is fully converted to a metal
oxide.
[0226] Converting a metal compound composition comprising at least
one metal salt of a carboxylic acid, according to some embodiments
of the present invention, comprises exposing the metal compound
composition to an environment operable to convert the at least one
metal salt to at least one metal oxide. Environments operable to
convert metal compounds to metal oxides, in some embodiments,
provide conditions sufficient to vaporize and/or decompose the
compound moieties and precipitate metal oxide formation. In one
embodiment, an environment operable to convert metal compounds to
metal oxides comprises a heated environment. A metal salt of a
carboxylic acid, for example, can be exposed to an environment
heated to a temperature operable to convert the carboxylic acid and
induce formation of the metal oxide. In some embodiments, the
environment is heated to a temperature greater than about
400.degree. C. In some embodiments, the environment is heated to a
temperature up to about 425.degree. C. or up to about 450.degree.
C. In other embodiments, the environment is heated to a temperature
ranging from about 400.degree. C. to about 650.degree. C. In a
further embodiment, the environment is heated to a temperature
ranging from about 400.degree. C. to about 550.degree. C.
[0227] In some embodiments, the metal compound composition
penetrates into the substrate of the first electrode to a depth
ranging from about 10 nm to about 100 nm or from about 20 nm to
about 80 nm. In other embodiments, the metal compound composition
penetrates into the substrate of the first electrode to a depth
ranging from about 30 nm to about 60 nm or from about 40 nm to
about 50 nm. Converting the metal compound on the substrate of the
first electrode to a metal oxide, in some embodiments, produces an
electrode-electrolyte transition layer comprising electrolyte metal
oxide material and electrode substrate material.
[0228] In other embodiments, the metal compound composition does
not penetrate into the porous structure of the electrolyte and an
abrupt interface exists between the electrode and the
electrolyte.
[0229] Moreover, exposing metal compound compositions to
environments operable to convert the compositions to metal oxides,
as provided herein, eliminates the need for sintering to produce
metal oxides. By eliminating sintering, solid oxide cell production
methods of the present invention gain several advantages. One
advantage is that the lower temperatures of some methods of the
present invention do not induce grain growth or other degradative
processes in various layers of the solid oxide cell during
production. Another advantage is that the compound compositions
permit tailoring of individual metal oxide layers in the
construction of electrolytes and electrodes. Methods of the present
invention, for example, permit one metal oxide layer of an
electrolyte or electrode to have completely different compositional
and/or physical parameters in comparison to an adjacent metal oxide
layer, in some embodiments. Such control over the construction of
electrolytes and electrodes of solid oxide cells is extremely
difficult and, in many cases, not possible with present sintering
techniques.
[0230] In another embodiment, a method of making a solid oxide cell
comprises providing a first electrode and depositing at least one
electrolyte layer on the first electrode, wherein depositing at
least one electrolyte layer comprises applying a metal compound
composition to the first electrode, and converting at least some of
the metal compound composition to a metal oxide. A metal compound
composition can comprise a solid, liquid, or vapor metal compound
composition as provided herein. In some embodiments, more than one
metal compound composition is applied before conversion.
[0231] In some embodiments, a plurality of electrolyte layers are
stacked on the first electrode. A method of producing a solid oxide
cell, in one embodiment, comprises providing a first electrode and
stacking a plurality of electrolyte layers on the first electrode,
wherein each layer of electrolyte is stacked on a preceding layer
by applying a metal compound composition to the preceding layer.
The metal compound composition is subsequently converted to a metal
oxide. In another embodiment, the repetition of multiple layers of
electrolyte depositions is used to gradually add a particular
nano-scale thickness of electrolyte onto the first electrode that
serves, in this case, as the body or substrate for the deposited
thin film of electrolyte. In one embodiment, the preceding layer
comprises the first electrode. In another embodiment, the preceding
layer comprises one of the plurality of electrolyte layers.
[0232] In some embodiments of methods for making solid oxide cells,
a second electrode is deposited on the opposite surface of the
electrolyte so that the electrolyte becomes the central layer
between the two outer electrodes. The successive building up of
thin film layers (from first electrode to electrolyte to second
electrode) completes the construction of the solid oxide cell. In
one embodiment, a second electrode is deposited on an electrolyte
by applying a metal compound composition to the electrolyte,
contacting the metal compound composition with the second
electrode, and converting at least some of the metal compound
composition to a metal oxide composition. In some embodiments, the
metal compound composition is fully converted to a metal oxide.
[0233] Converting a metal compound composition comprising at least
one metal salt of a carboxylic acid in the deposition of a second
electrode, according to some embodiments of the present invention,
comprises exposing the metal compound composition to an environment
capable of converting at least one metal salt to at least one metal
oxide as described herein. Converting other metal compositions,
such as metal alkoxides, metal .beta.-diketonates, combinations
thereof, and combinations thereof including at least one metal
carboxylate in some embodiments, also comprises exposing the metal
composition to an environment capable of converting the metal
compounds in the composition to at least one metal oxide.
[0234] The conversion environment, for various embodiments of the
present invention, can be any suitable environment, and the
conversion can be precipitated by any suitable means. In some
embodiments of the present invention, the substrate is heated; in
others, the atmosphere about the metal compound composition is
heated; in still others, the metal compound composition is heated.
In further embodiments, a substrate having a metal compound
composition deposited thereon can be heated in an oven, or exposed
to heated gas. The conversion environment may also be created using
induction heating through means familiar to those skilled in the
art of induction heating. Alternatively, the conversion environment
may be provided using a laser applied to the surface area for
sufficient time to allow at least some of the metal compounds to
convert to metal oxides. In other applications, the conversion
environment may be created using an infra-red light source which
can reach sufficient temperatures to convert at least some of the
metal compounds to metal oxides. Some embodiments may employ a
microwave emission device to cause at least some of the metal
compound to convert. Other embodiments provide a plasma to heat the
metal compound. In the case of induction heating, microwave
heating, lasers, plasmas, and other heating methods that can
produce the necessary heat levels in a short time, for example,
within seconds, 1 minute, 10 minutes, 20 minutes, 30 minutes, 40
minutes, or one hour.
VIII. Methods of Making Electrodes
[0235] In addition to solid oxide cells, the present invention
provides methods of making electrodes. In one embodiment, a method
of making an electrode comprises providing a substrate and
depositing at least one metal oxide layer on the substrate wherein
depositing comprises applying a metal compound composition to the
substrate, and converting at least some of the metal compound
composition to a metal oxide composition. In some embodiments, the
metal compound composition is fully converted to at least one metal
oxide.
[0236] In some embodiments, a plurality of metal oxide layers are
deposited on the substrate. In one embodiment, for example, a
method of making an electrode comprises depositing a plurality of
metal oxide layers on the substrate, wherein each layer of metal
oxide is deposited on a preceding layer by applying a metal
compound composition to the preceding layer. The metal compound
composition is subsequently converted to at least one metal
oxide.
[0237] In some embodiments, the metal compound composition
penetrates into the substrate to a depth ranging from about 3 nm to
about 100 nm or from about 20 nm to about 80 nm. In other
embodiments, the metal compound composition penetrates into the
substrate to a depth ranging from about 30 nm to about 60 nm or
from about 40 nm to about 50 nm. Converting the metal compound on
the substrate to a metal oxide, in some embodiments, produces the
substrate-coating transition layer comprising substrate material
and metal oxide coating material. In some embodiments, the metal
compound composition does not penetrate the substrate and an abrupt
interface exists between the substrate and coating.
[0238] Metal compound compositions suitable for use in methods of
making electrodes are consistent with any of the metal compound
compositions described hereinabove for use in methods of making
solid oxide cells. Moreover, metal compound compositions can be
applied and converted to metal oxide compositions in any manner
consistent with the same recited herein for methods of making solid
oxide cells.
IX. Methods of Making Interconnects
[0239] In addition to solid oxide cells, the present invention
provides methods of making interconnects. In one embodiment, a
method of making an interconnect comprises providing a substrate
and depositing at least one metal oxide layer on the substrate
wherein depositing comprises applying a metal compound composition
to the substrate, and converting at least some of the metal
compound composition to a solid oxide composition. In some
embodiments, the metal compound composition is fully converted to
at least one metal oxide.
[0240] In some embodiments, a plurality of metal oxide layers are
deposited on the substrate. In one embodiment, for example, a
method of making an interconnect comprises depositing a plurality
of metal oxide layers on the substrate, wherein each layer of metal
oxide is deposited on a preceding layer by applying a metal
compound composition to the preceding layer. That metal compound
composition is subsequently converted to at least one metal
oxide.
[0241] In some embodiments, the metal compound composition
penetrates into the substrate to a depth ranging from about 3 nm to
about 100 nm or from about 20 nm to about 80 nm. In other
embodiments, the metal compound composition penetrates into the
substrate to a depth ranging from about 30 nm to about 60 nm or
from about 40 nm to about 50 nm. Converting the metal compound on
the substrate to a metal oxide, in some embodiments, produces a
substrate-coating transition layer comprising substrate material
and metal oxide coating material. In some embodiments, the metal
compound composition does not penetrate the porous structure of the
substrate and an abrupt interface exists between the substrate and
coating.
[0242] Metal compound compositions suitable for use in methods of
making interconnects are consistent with any of the metal compound
compositions described hereinabove for use in methods of making
solid oxide cells. Moreover, metal compound compositions can be
applied and converted to metal oxide compositions in any manner
consistent with the same recited herein for methods of making solid
oxide cells.
X. Methods of Increasing Ionic Conductivity and Triple Phase
Boundaries
[0243] Through the greatly-increased thinness of the thin film
electrolyte and through the extremely small size of the
crystallites within the thin film electrolyte of some embodiments,
the present invention allows for a solid electrolyte to be
constructed that is both very conductive to ions (such as anionic
oxygen)--and yet, to provide a thin film electrolyte that is
sufficiently dense to act as the central barrier layer between, for
example, the fuel electrode (anode) and the air electrode (cathode)
of a solid oxide fuel cell.
[0244] The very thinness of the electrolyte (from 0.3 to 3.0
microns, in some embodiments) inherently allows for greater ionic
conductivity of oxygen anions. Thus, the extremely small size of
the crystallites may provide a greater density (and freedom from
defects and pin-holes) that would be impossible were the
crystallite size to be much larger.
[0245] In another aspect, the present invention provides methods of
increasing the ionic conductivity of a solid electrolyte. A method
of increasing the ionic conductivity of a solid electrolyte, in
some embodiments, comprises increasing the number of grain
boundaries in the solid electrolyte, wherein increasing the number
of grain boundaries comprises forming a plurality of
nanocrystalline grains comprising an electrolyte material. In some
embodiments of the present invention, an electrolyte material
comprises one or more metal oxides. Moreover, forming a plurality
of metal oxide nanocrystalline grains comprises applying a metal
compound composition to a substrate, and converting at least some
of the metal compound composition to a plurality of metal oxide
nanocrystalline grains. In some embodiments, ionic conductivity
comprises oxygen ion conductivity.
[0246] In another aspect, the present invention provides methods of
increasing the number of triple phase boundaries in a solid oxide
cell comprising providing a solid electrolyte comprising a
plurality of metal oxide nanocrystalline grains. Providing a solid
electrolyte comprising a plurality of nanocrystalline grains, in
some embodiments, comprises applying a metal compound composition
to a substrate, and converting at least some of the metal compound
composition to a plurality of metal oxide nanocrystalline grains.
In some embodiments, the metal compound composition is fully
converted into a plurality of metal oxide nanocrystalline grains.
In one embodiment, the substrate comprises an electrode of the
solid oxide cell.
[0247] In some embodiments of the present invention,
nanocrystalline grains have an average size less than about 50 nm.
In one embodiment, nanocrystalline grains of electrolyte layers
have an average size ranging from about 1 nm to about 40 nm or from
about 5 nm to about 30 nm. In another embodiment, nanocrystalline
grains have an average size ranging from about 10 nm to about 25
nm. In a further embodiment, nanocrystalline grains have an average
size less than about 10 nm or less than about 5 nm.
[0248] Metal compound compositions suitable for use in methods of
increasing ionic conductivity and/or the number of triple phase
boundaries are consistent with any of the metal compound
compositions described hereinabove for use in methods of making
solid oxide cells. Moreover, metal compound compositions can be
applied and converted to metal oxide compositions in any manner
consistent with the same recited herein for methods of making solid
oxide cells.
XI. Methods of Reducing Differences in Coefficients of Thermal
Expansion
[0249] In a further aspect, the present invention provides methods
of reducing differences in coefficients of thermal expansion
between an electrode and a solid electrolyte of a solid oxide cell.
In one embodiment, a method of reducing differences in coefficients
of thermal expansion between an electrode and a solid electrolyte
comprises interposing an electrode-electrolyte transition layer
between the electrode and the solid electrolyte. Interposing an
electrode-electrolyte transition layer between the electrode and
the solid electrolyte comprises applying an electrolyte composition
comprising a metal compound composition to the electrode, and
converting at least some of the metal compound to at least one
metal oxide.
[0250] Metal compound compositions suitable for use in methods of
reducing differences in coefficients of thermal expansion between
an electrode and a solid electrolyte of a solid oxide cell are
consistent with any of the metal compound compositions described
hereinabove for use in methods of making solid oxide cells.
Moreover, metal compound compositions can be applied and converted
to metal oxide compositions in any manner consistent with the same
recited herein for methods of making solid oxide cells.
XII. Application of Metal Layers
[0251] In some embodiments of solid oxide cells, electrodes, and/or
interconnects of the present invention, metal layers, as opposed to
metal oxide layers, are produced. In one embodiment, a method of
producing a metal layer comprises providing a substrate and
depositing at least one metal layer on the substrate wherein
depositing comprises applying a metal compound composition to the
substrate, and converting at least some of the metal compound
composition to a metal layer. In some embodiments, the metal
compound composition is fully converted to a metal layer.
Converting the metal compound composition to a metal layer, in some
embodiments, comprises exposing the metal compound composition to
an environment operable to convert the at least one metal salt to a
metal. Environments operable to convert metal compounds to a metal
layer, in some embodiments, comprise reducing environments
including, but not limited to, a hydrogen atmosphere ranging from
200.degree. C. to 1200.degree. C. or higher. Additional reducing
environments known to one of skill in the art also are
contemplated. In further embodiments, the at least one metal
compound is converted into at least one metal oxide, which is then
exposed to a reducing environment and at least partially converted
into at least one metal. In still further embodiments, a contiguous
metal layer forms, while in other embodiments, non-contiguous metal
sites appear. In some embodiments, a substrate comprises a metal.
In other embodiments, a substrate comprises a metal oxide, such as
a metal oxide layer. In still other embodiments, a substrate
comprises some other material, such as, for example, one or more
polymers, ceramics, composites, cermets, or a combination
thereof.
XIII. Methods of Generating Electric Current
[0252] In yet another aspect, the present invention provides a
method of generating electric current comprising providing a solid
oxide fuel cell comprising an air electrode, a fuel electrode, an
electrolyte interposed between the air electrode and the fuel
electrode, and at least one electrode-electrolyte transition layer;
providing a fuel to the fuel electrode; providing oxygen to the air
electrode; oxidizing the fuel to generate free electrons;
transporting the free electrons through an external circuit to the
air electrode (cathode); and then reducing the diatomic oxygen
molecules at the air electrode to oxygen anions. In some
embodiments, the fuel comprises hydrogen. In other embodiments, the
fuel comprises at least one hydrocarbon. In embodiments wherein the
fuel is a hydrocarbon, methods of generating electrical current
further comprise reforming the hydrocarbon fuel at the fuel
electrode.
[0253] FIG. 2 illustrates a solid oxide fuel cell according to one
embodiment of the present invention. As displayed in FIG. 2, the
solid oxide fuel cell (210) comprises an air electrode (cathode)
(220), a fuel electrode (anode) (230), an electrolyte (240)
interposed between the air electrode (cathode) (220) and the fuel
electrode (anode) (240). An electrode-electrolyte transition layer
(not shown) is interposed between the air electrode (cathode) (220)
and the electrolyte (240). The air electrode (cathode) (220) and
the fuel electrode (anode) (230) are connected by an external
circuit (250) across which a load (260) is applied. Oxygen
(O.sub.2) (270) or a mixture of gases comprising oxygen (e.g., air)
is fed to the air electrode (220) wherein oxygen molecules (270)
are reduced to oxygen anions (O.sup.2) (280). Moreover, hydrogen
molecules (H.sub.2) (290) from a fuel source are oxidized at the
fuel electrode (230). Electrons (300) removed from hydrogen
molecules (290) at the fuel electrode (230) travel through the
external circuit (250) to the air electrode (cathode) (220)
generating electric current while oxygen anions (O.sup.2) (280)
travel through the electrolyte (240) to combine with hydrogen
cations (H.sup.+) (not shown) thereby producing water (H.sub.2O)
(310). Unused oxygen (320) exits the cell (210) after passing
through the air electrode (220), while water (310) exits the cell
(210) from the fuel electrode (230).
[0254] In other embodiments of the present invention, various
configurations of fuel cells are contemplated. For example, more
than one fuel electrode can pair with more than one air electrode.
The physical configuration of the various electrodes, electrolytes,
interconnects, and/or other components is not limited. In some
embodiments, the configuration is optimized for size, current
density, voltage, portability, fuel versatility, energy
conservation, specific application, aesthetics, other
considerations, or combinations thereof.
Example 1--LSM Electrode
[0255] LSM planar electrodes can be purchased or formed as follows.
LSM powder, available from American Elements
(www.AmericanElements.com) is mixed with 5-10% wt. corn starch,
compression molded into a flat disk shape not less than about
1/16th of an inch, and sintered at 1200.degree. C. for 30 minutes
in air. The resulting porous material is suitable for use as a
cathode in a fuel cell embodying aspects of the present
invention.
[0256] A two-inch diameter, approximately 2 mm thick LSM disc
having an average pore size of about 15 .mu.m and porosity of about
30% was formed in accordance with the foregoing procedure and
polished with diamond paste to a roughness of approximately 1
.mu.m. The polished surface was held against a 0.1 L volume vacuum
chamber opening with an O-ring, and a vacuum was applied to measure
the rate at which vacuum is lost through the porous electrode. A
pressure of no less than 1200 mtorr was measured in the vacuum
chamber, whereupon a valve between the vacuum chamber and a vacuum
pump was closed. The pressure in the vacuum chamber returned
rapidly to ambient pressure. See Table 1.
Example 2--First Five Layers of YSZ Electrolyte with YSZ
Nanoparticles and Powder
[0257] A viscous composition was made as follows. First, a liquid
composition containing yttrium (III) 2-ethylhexanoate (15 molar %
based on Y) and zirconium (IV) 2-ethylhexanoate (85 molar % based
on Zr) was made. Then, one part of the liquid composition by weight
was mixed with one part of YSZ nanoparticles having an average
particle size of 50-100 nm; one part of the liquid composition was
mixed with one part of YSZ powder having an average particle size
of about 1 .mu.m; and one part of the liquid composition was mixed
with one part of YSZ powder having an average particle size of
about 45 .mu.m. All three mixtures were combined to form the
viscous composition.
[0258] The LSM electrode from Example 1 was wetted on the polished
surface with the viscous composition. The wet electrode was placed
in a room-temperature electric furnace in air and the oven was
heated to 450.degree. C. Once the oven reached 450.degree. C. in
about 15 minutes, the oven was turned off, taking another 15
minutes to cool back to room temperature. The cooled electrode, now
coated with a layer of YSZ electrolyte was subjected to the vacuum
loss test described in Example 1. Without wishing to be bound by
theory, it is believed that including the YSZ nanoparticles and
powder in the composition applied to the surface of the electrode
helps close the pores at the surface of the electrode.
[0259] Four more layers of the YSZ electrolyte with the YSZ
nanoparticles and powder were formed by applying the viscous
composition to the cooled electrode, heating and cooling the
electrode as described above, and repeating. After each applying,
heating and cooling, the electrode was subjected to the vacuum loss
test described in Example 1.
Example 3--Subsequent Layers of YSZ Electrolyte
[0260] The room-temperature electrode of Example 2 was coated
repeatedly with a liquid composition containing yttrium (III)
2-ethylhexanoate (15 molar % based on Y) and zirconium (IV)
2-ethylhexanoate (85 molar % based on Zr) (and no nanoparticles or
powder). After each application of the liquid composition, the
electrode was heated and cooled as described in Example 2, and
tested for vacuum loss as described in Example 1.
TABLE-US-00001 TABLE 1 Vacuum Loss Data Number of Pressure Time to
Equal Leak Rate Coats (mtorr) Pressure (s) (L*Torr/s) 0 1200 n/a
n/a 1 800 n/a n/a 2 750 7 1.09E+01 3 675 23 3.30E+00 4 600 30
2.53E+00 5 550 25 3.04E+00 6 600 30 2.53E+00 7 500 33 2.30E+00 8
400 47 1.62E+00 9 300 83 9.16E-01 10 260 105 7.24E-01 11 200 132
5.76E-01 12 155 180 4.22E-01 13 145 225 3.38E-01 14 150 180
4.22E-01 15 145 645 1.18E-01 16 130 705 1.08E-01 17 120 3240
2.35E-02 18 110 2880 2.64E-02 19 93 3300 2.30E-02 20 70 10320
7.36E-03
Example 4--Extrapolation
[0261] Using the leakage rates measured in Table 1, it is possible
to extrapolate the leakage rates to hypothetical samples having
more coats of YSZ electrolyte. Table 2 shows estimated time for one
pound of Freon (CCl.sub.2F.sub.2) to leak through YSZ-coated LSM
samples having the same leakage rate behavior as the electrode
prepared in Examples 1-3.
TABLE-US-00002 TABLE 2 Extrapolation for Freon Leakage Number of
Leak Rate Time for 1 lb. Freon Coats (L*torr/s) to leak 15 1.00E-01
10 days 21 1.00E-02 3 months 27 1.00E-03 2.7 years 33 1.00E-04 27
years 39 1.00E-05 270 years 46 1.00E-06 2,700 years 52 1.00E-07
27,000 years 58 1.00E-08 270,000 years 64 1.00E-09 2,700,000 years
70 1.00E-10 27,000,000 years
[0262] From the foregoing data, it is believed that approximately
thirty coats of YSZ electrolyte applied as set forth in Examples
1-3 should be sufficient for certain solid oxide cell embodiments
of the present invention. Other embodiments may require more or
fewer coats. Still other embodiments may tolerate faster, or
require slower, leak rates.
Example 5--Forming Solid Oxide Fuel Cell
[0263] An electrode having several coats of electrolyte as made
according to Examples 1-3 can be assembled into a cell with a
porous nickel-YSZ cermet electrode. The Ni--YSZ electrode can be
purchased or manufactured as explained in Example 1. Ni--YSZ cermet
powders are also available from American Elements. A Ni--YSZ disk
having 2'' diameter and approximately 2 mm thickness can be placed
onto a LSM disk having 20-40 layers of YSZ electrolyte coated
thereon as described in Examples 2-3, along with an application of
the liquid composition described in Example 3 on the YSZ. Then the
Ni--YSZ/YSZ/LSM sandwich is heated as described in Example 2. Upon
heating, the liquid composition will form additional YSZ that will
bond the Ni--YSZ disk to the YSZ electrolyte and LSM electrode. The
bonded sandwich can be assembled into a fuel cell adapted to supply
a hydrogen-containing gas to the Ni--YSZ electrode to act as an
anode, and to supply an oxygen-containing gas to the LSM electrode
to act as a cathode. Interconnects connecting the anode and cathode
to external wiring are adapted to complete the electrical circuit.
When the fuel cell is heated to 800.degree. C. and the
hydrogen-containing gas and oxygen-containing gas are supplied, the
cell should produce electricity, as shown in FIG. 2.
EMBODIMENTS
Embodiment 1
[0264] A solid oxide cell or a component thereof comprising:
at least one metal oxide proximal to at least one substrate, and a
transition layer interposed between the at least one metal oxide
and the at least one substrate.
Embodiment 2
[0265] The solid oxide cell or component thereof as set forth in
claim 1, wherein the transition layer has a thickness ranging from
about 3 nm to about 100 nm.
Embodiment 3
[0266] The solid oxide cell or component thereof as set forth in
embodiment 2, wherein the transition layer has a thickness less
than about 10 nm.
Embodiment 4
[0267] The solid oxide cell or component thereof as set forth in
embodiment 1, further comprising:
at least one compositional gradient.
Embodiment 5
[0268] The solid oxide cell or component thereof as set forth in
embodiment 4, wherein the at least one compositional gradient
comprises electrode material present in a metal oxide
electrolyte.
Embodiment 6
[0269] The solid oxide cell or component thereof as set forth in
embodiment 1, further comprising at least one catalytic
material.
Embodiment 7
[0270] The solid oxide cell or component thereof as set forth in
embodiment 6, wherein the at least one catalytic material is chosen
from platinum, palladium, rhodium, nickel, cerium, gold, silver,
zinc, lead, ruthenium, rhenium, and mixtures thereof.
Embodiment 8
[0271] The solid oxide cell or component thereof as set forth in
embodiment 6, wherein the component is chosen from electrodes,
electrolytes, and interconnects.
Embodiment 9
[0272] The solid oxide cell or component thereof as set forth in
embodiment 1, wherein the metal oxide cell is chosen from metal
oxide fuel cells, metal oxide electrolyzer cells, and sensors.
Embodiment 10
[0273] A method of making a metal oxide cell or a component thereof
comprising at least one metal oxide, comprising:
applying at least one metal compound to a substrate, and converting
at least some of the at least one metal compound to at least one
metal oxide.
Embodiment 11
[0274] The method of embodiment 10, further comprising depositing a
plurality of metal oxide layers on the substrate.
Embodiment 12
[0275] The method of embodiment 10, further comprising applying at
least one nanoparticle to the substrate before the converting.
Embodiment 13
[0276] An electrolyte adaptable for use in a metal oxide cell,
comprising:
a plurality of metal oxide nanocrystalline grains having an average
size of less than about 50 nm; and wherein the electrolyte has a
porosity less than about 5%.
Embodiment 14
[0277] The electrolyte of embodiment 13, wherein the electrolyte is
substantially non-porous.
Embodiment 15
[0278] The electrolyte of embodiment 13, wherein the electrolyte
has a thickness less than about 1 .mu.m.
Embodiment 16
[0279] The electrolyte of embodiment 13, wherein the metal oxide
nanocrystalline grains have an average size of less than about 10
nm.
Embodiment 17
[0280] The electrolyte of embodiment 13, wherein the plurality of
metal oxide nanocrystalline grains comprise yttria-stabilized
zirconia.
Embodiment 18
[0281] The electrolyte of embodiment 13, wherein the plurality of
metal oxide nanocrystalline grains comprise lanthanum strontium
doped manganite.
Embodiment 19
[0282] A method of preparing an electrolyte adaptable for use in a
metal oxide cell, comprising: applying at least one metal compound
to a substrate; and converting at least some of the at least one
metal compound to form a plurality of metal oxide nanocrystalline
grains.
Embodiment 20
[0283] The method of embodiment 19, wherein the converting
comprises heating the environment of the at least one metal
compound to a temperature greater than about 400.degree. C.
Embodiment 21
[0284] The method of embodiment 20, wherein the environment is
heated to a temperature ranging from about 400.degree. C. to about
650.degree. C.
Embodiment 22
[0285] The method of embodiment 20, wherein the environment is
heated to a temperature of up to about 450.degree. C.
Embodiment 23
[0286] A method for detecting at least one analyte, comprising:
providing at least one sensor for the at least one analyte, wherein
the at least one sensor comprises at least one metal oxide made by
a process comprising:
[0287] applying at least one metal oxide to a substrate, and
[0288] converting at least some of the at least one metal compound
to the at least one metal oxide; and
passing at least one ion through the at least one metal oxide to
detect the at least one analyte.
Embodiment 24
[0289] The method of embodiment 23, wherein the at least one
analyte is chosen from O.sub.2, CO, CO.sub.2, H.sub.2, NO.sub.N,
SO.sub.N, H.sup.+, K.sup.+, Na.sup.+, and glucose.
Embodiment 25
[0290] The method of embodiment 23, wherein the at least one
analyte is oxygen.
[0291] Various embodiments of the invention have been described in
fulfillment of the various objects of the invention. It should be
recognized that these embodiments are merely illustrative of the
principles of the present invention, and do not imply limitation.
Furthermore, the foregoing description of various embodiments does
not necessarily imply exclusion. For example, "some" embodiments
may include all or part of "other" and "further" embodiments.
Furthermore, "a" can mean "one or more than one," and does not
necessarily mean "one and only one." Numerous modifications and
adaptations thereof will be readily apparent to those skilled in
the art without departing from the spirit and scope of the
invention.
* * * * *
References